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shanghai Tauto Biotech Co., Ltd

The quality is guaranteed. If you find the product is wrong compared with COA, we promise 100% refund or change product. COA and HPLC will be shipped out with goods. You can also inform your analysis method and we will follow your analysis method

Tetrodotoxin E-2968

Cas:4368-28-9

Min.Order:0 Metric Ton

Negotiable

Type:Manufacturers

inquiry

Dayang Chem (Hangzhou) Co.,Ltd.

Dayangchem's R&D center can offer custom synthesis according to the contract research and development services for the fine chemicals, pharmaceutical, biotechnique and some of the other chemicals. DayangChem can provide different quantities

Tetrodotoxin

Cas:4368-28-9

Min.Order:1 Kilogram

FOB Price: $3.0

Type:Lab/Research institutions

inquiry

Xi'an Xszo Chem Co., Ltd.

1. Factory price and high quality must be guaranteed, base on 8 years of production and R&D experience2. Free samples will be provided,ensure specifications and quality are right for customer3. Customers will receive the most professional technical s

Xi`an Eastling Biotech Co., Ltd.

TETRODOTOXIN CAS: 4368-28-9 Molecular Formula: C11H17N3O8 Home Product Category 4368-28-9 4368-28-9 - Names and Identifiers Name TETRODOTOXIN Synonyms TETRODOTOXIN PUFFERFISHTOXIN PUFFERFISHPOISONING Tetrodo

Factory high quality Tetrodotoxin

Cas:4368-28-9

Min.Order:1 Gram

FOB Price: $5.0 / 7.0

Type:Trading Company

inquiry

Chemwill Asia Co., Ltd.

Our main production base is located in Xuzhou industry park. We are certified both to the ISO 9001 and ISO 14001 Standards, have a safety management system in place.Our R&D team masters core technology for process-design of target building block

Tetrodotoxin

Cas:4368-28-9

Min.Order:5 Kiloliter

FOB Price: $1.2 / 5.0

Type:Manufacturers

inquiry

Hebei Nengqian Chemical Import and Export Co., LTD

With our good experience, we offer detailed technical support and advice to assist customers. We communicate closely with customers to establish their quality requirements. Consistent Quality Our plant has strict quality control in each manufacturin

Tetrodotoxin CAS 4368-28-9

Cas:4368-28-9

Min.Order:1 Kilogram

FOB Price: $70.0 / 90.0

Type:Trading Company

inquiry

Shanghai Upbio Tech Co.,Ltd

1.No Less 8 years exporting experience. Clients can 100% received goods 2.Lower Price with higher quality 3,Free sample 4,We are sincerely responsible for the "product quality" and "After Service" Upbio is Specialized

Qingdao Beluga Import and Export Co., LTD

Beluga chemical professional supply Tetrodotoxin CAS 4368-28-9 Why choose Beluga chemical 1. Beluga Chemical has a professional RESEARCH and development team and strong technical force to ensure technical support and research capabilities. 2. M

Tetrodotoxin CAS 4368-28-9

Cas:4368-28-9

Min.Order:1 Gram

Negotiable

Type:Lab/Research institutions

inquiry

Shandong Hanjiang Chemical Co., Ltd.

Hello, dear friend! I'm Hansen and Allen from China. Welcome to my lookchem mall! The following is a brief introduction of our company's products and services. If you are interested in our products, please contact us by emai

Hangzhou JINLAN Pharm-Drugs Technology Co., Ltd

Specification:USP/EP Month production ablity:50kg/Month Low price& High quality Manufacturer Appearance:white powder Storage:Room Temperature Package:in aluminum bag and foil bag or as customers' require Application:4368-28-9 Transportati

tetrodotoxin

Cas:4368-28-9

Min.Order:1 Metric Ton

Negotiable

Type:Trading Company

inquiry

Henan Wentao Chemical Product Co., Ltd.

Henan Wentao Chemical Product Co.,Ltd is Located in Zhengzhou High-tech Development Zone with import and export license, We passed ISO 9001:2008 as well, Henan Wentao has developed more than 1000 compounds, which are widely used in the fields of prod

Triumph International Development Limilted

Lorcaserin(856681-05-5)is an orally administered agent and a selective 5-HT2C receptor agonist for the treatment of obesity. It had been approved for marketing in US by FDA on 27 June in 2012. In clinical studies, lorcaserin h

Tetrodotoxin

Cas:4368-28-9

Min.Order:100 Metric Ton

Negotiable

Type:Lab/Research institutions

inquiry

Chengdu Biopurify Phytochemicals Ltd.

Chengdu Biopurify Phytochemicals Ltd. is a leading company in the research, development, manufacture and marketing of High Quality Phytochemicals and Extracts(especially Active Ingredients from Traditional Chinese Medicine,Traditional Chinese Medic

Tetrodotoxin

Cas:4368-28-9

Min.Order:0 Metric Ton

Negotiable

Type:Lab/Research institutions

inquiry

Hangzhou J&H Chemical Co., Ltd.

J&H CHEM R&D center can offer custom synthesis according to the contract research and development services for the fine chemicals, pharmaceutical, biotechnique and some of the other chemicals. J&H CHEM has some Manufacturing base in Jia

Shaanxi Cuicheng Biomedical Technology Co., Ltd.

Why Choose Us: 1. Factory direct sales, so we can provide the competitive price and high quality product base on 8 years of production and R&D experience. 2. It is available in stock for quick shipment.Products could be packaged according to cu

TETRODOTOXIN

Cas:4368-28-9

Min.Order:1 Gram

Negotiable

Type:Other

inquiry

Zibo Hangyu Biotechnology Development Co., Ltd

Zibo Hangyu Biotechnology Development Co., Ltd is a leading manufacturer and supplier of chemicals in China. We develop produce and distribute high quality pharmaceuticals, intermediates, special chemicals and OLED intermediates and other fine chemi

High qualityTetrodotoxin

Cas:4368-28-9

Min.Order:10 Gram

FOB Price: $100.0

Type:Lab/Research institutions

inquiry

Hangzhou Lingrui Chemical Co.,Ltd.

favourable price of Tetrodotoxin 4368-28-9 top quality supplierAppearance:powde Storage:Store in cool and dry place. Package:according to customers' requirements Application:Multipurpose intermediate Transportation:By air(EMS or EUB or FedEx or TN

favourable price of Tetrodotoxin 4368-28-9 top quality supplier

Cas:4368-28-9

Min.Order:1 Gram

Negotiable

Type:Other

inquiry

HANGZHOU YUNUO CHEMICAL CO.,LTD

Superior quality, moderate price & quick delivery. Appearance:white powder Storage:Stored in cool, dry and ventilation place; Away from fire and heat Package:25kg/drum, or as per your request. Application:Used as Pharmaceutical Intermediates Tr

Pribolab PTE.LTD

We can offer products of different specifications Appearance:bottle Storage:-20℃ Application:Determination of corresponding toxins

Tetrodotoxin

Cas:4368-28-9

Min.Order:0 Metric Ton

Negotiable

Type:Trading Company

inquiry

Jiangsu Qianyu Molecular Technology Co., LTD.

Our Advantages A. International Top level TechnologyOur company owned biomedicine experts are famous at home and abroad with rich experience in research and development in the field of efficient chiral functional molecules research and development an

High Purity TETRODOTOXIN

Cas:4368-28-9

Min.Order:0

Negotiable

Type:Trading Company

inquiry

EAST CHEMSOURCES LIMITED

factory?direct?saleAppearance:White Powder Storage:Store In Dry, Cool And Ventilated Place Package:25kg/drum, also according to the clients requirement Application:It is widely used as a thickener, emulsifier and stabilizer Transportation:By Sea Or B

Tetrodotoxin CAS NO.4368-28-9

Cas:4368-28-9

Min.Order:1 Kilogram

FOB Price: $18.0 / 20.0

Type:Trading Company

inquiry

Zibo Dorne chemical technology co. LTD

Product Details Grade: pharmaceutical grade Purity:99%+ ProductionCapacity: 1000 Kilogram/Month Scope of use: For scientific research only(The product must be used legally) Our Advantage 1. Best quality with competitive price. 2. Quick shipping,

TETRODOTOXIN

Cas:4368-28-9

Min.Order:1 Kilogram

Negotiable

Type:Lab/Research institutions

inquiry

Hangzhou Huarong Pharm Co., Ltd.

Hangzhou Huarong Pharm Co., Ltd.established since 2006 , has been actively developing specialty products for Finished Dosages, APIs, Intermediates, and Fine chemicals markets in North America, Europe, Korea, Japan, Mid-East and all over the World. Hu

Tetrodotoxin

Cas:4368-28-9

Min.Order:0

Negotiable

Type:Trading Company

inquiry

TAIZHOU ZHENYU BIOTECHNOLOGY CO., LTD

Zhenyu biotech exported this product to many countries and regions at best price. if you are looking for the material's manufacturer or supplier in china, zhenyu biotech is your best choice. pls contact with us freely for getting detailed

TETRODOTOXIN

Cas:4368-28-9

Min.Order:1 Kilogram

FOB Price: $2.0

Type:Lab/Research institutions

inquiry

Hangzhou Fandachem Co.,Ltd

Hangzhou Fanda Chemical Co.,Ltd (FandaChem) , a China-based chemical company, specialize in exporting Tetrodotoxin;TTX CAS:4368-28-9, Please contact us by email freely. We are leading exporter in China. If you really need this cargo,

Tetrodotoxin;TTX CAS:4368-28-9 from fandachem

Cas:4368-28-9

Min.Order:0 Metric Ton

Negotiable

Type:Other

inquiry

Shandong Mopai Biotechnology Co., LTD

Shandong Mopai Biotechnology Co., LTD is a leading manufacturer and supplier of chemicals in China. We develop produce and distribute high quality pharmaceuticals, intermediates, special chemicals and OLED intermediates and other fine chemicals. W

Tetrodotoxin CAS NO.4368-28-9

Cas:4368-28-9

Min.Order:1 Gram

Negotiable

Type:Lab/Research institutions

inquiry

KAISA GROUP INC

1.Applied in food field.it can improve the immune system and prolong life. 2.Appliedin cosmetic field.it can improve the skin care. 3.Applied in pharmaceutical field.it can treat various dieases. 4.Our product quality assurance will make our customer

Tetrodotoxin CAS NO.4368-28-9

Cas:4368-28-9

Min.Order:1 Metric Ton

FOB Price: $1.5

Type:Trading Company

inquiry

Golden Pharma Co., Limited

GOLDEN PHARMA CO.,LIMITED.is a professional pharmaceutical company,our team have more than 20years expereince in pharmaceutical production and sales. we are a professional technical enterprise specializing in the R & D, production,QA regulation

TETRODOTOXIN

Cas:4368-28-9

Min.Order:1 Kilogram

Negotiable

Type:Other

inquiry

Bluecrystal chem-union

We are a Union of chemistry in China, consists of chemists,engineers, laboratories,factories in China. We organize surplus capacity of R&D and production as well as custom synthesis for chemical products and chemical business project. We are supp

Tetrodotoxin CAS NO.4368-28-9

Cas:4368-28-9

Min.Order:1 Metric Ton

FOB Price: $1.0

Type:Trading Company

inquiry

Hebei Mojin Biotechnology Co.,Ltd

1, High quality with competitive price:2, Fast and safe delivery3.Excellent pre-sales and after-sales service4. Well-trained and professional technologist and sales with rich experience in the field for 5-10 yearsAppearance:see detailed specification

Synthetic route

C19H23N3O10

C19H23N3O10

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; for 3h;96.4%
4-O-methyltetrodotoxin

4-O-methyltetrodotoxin

A

tetradotoxin
4368-28-9

tetradotoxin

B

4,9-anhydro-4-epitetrodotoxin

4,9-anhydro-4-epitetrodotoxin

Conditions
ConditionsYield
In water-d2; trifluoroacetic acid for 96h;A 66%
B 15%
4,9-anhydro-4-epitetrodotoxin

4,9-anhydro-4-epitetrodotoxin

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
In water-d2; trifluoroacetic acid for 96h;63%
C28H49N3O12Si

C28H49N3O12Si

A

4,9-anhydrotetrodotoxin

4,9-anhydrotetrodotoxin

B

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
With trifluoroacetic acid In water at 20℃;A 58%
B 36%
C17H31NO8Si

C17H31NO8Si

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 2 steps
1: HgCl2; Et3N / dimethylformamide / 20 °C
2: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
Acetic acid (1R,3S,5S,6S,7S,8R,9S,10S)-9-acetoxy-9-acetoxymethyl-8-dimethoxymethyl-3,10-dihydroxy-7-(2,2,2-trichloro-acetylamino)-2,4-dioxa-tricyclo[3.3.1.13,7]dec-6-yl ester
794568-31-3

Acetic acid (1R,3S,5S,6S,7S,8R,9S,10S)-9-acetoxy-9-acetoxymethyl-8-dimethoxymethyl-3,10-dihydroxy-7-(2,2,2-trichloro-acetylamino)-2,4-dioxa-tricyclo[3.3.1.13,7]dec-6-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 4 steps
1: 2,6-lutidine / CH2Cl2 / 0 °C
2: diisobutylaluminum hydride / CH2Cl2 / -40 °C
3: HgCl2; Et3N / dimethylformamide / 20 °C
4: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1R,2S,5R,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-5,6-bis-triethylsilanyloxy-1-vinyl-cyclohex-3-enyl]-acetamide
794568-18-6

2,2,2-Trichloro-N-[(1R,2S,5R,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-5,6-bis-triethylsilanyloxy-1-vinyl-cyclohex-3-enyl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 16 steps
1.1: selenium dioxide; pyridine N-oxide / dioxane / Heating
1.2: 48 percent / NaBH4; CeCl3*7H2O / methanol / 0 °C
2.1: 2,6-lutidine / CH2Cl2 / 0 °C
2.2: 83 percent / m-chloroperbenzoic acid; Na2HPO4 / CH2Cl2 / 20 °C
3.1: 90 percent / O3; Et3N / CH2Cl2 / -78 °C
4.1: 70 percent / EtMgBr / tetrahydrofuran / 0 °C
5.1: 4-dimethylaminopyridine / pyridine / 20 °C
5.2: 91 percent / tetrabutylammonium fluoride / tetrahydrofuran / -10 °C
6.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
7.1: H2O2; NaHCO3 / methanol / 20 °C
8.1: 2,6-lutidine / CH2Cl2 / -40 °C
9.1: pyridine / 20 °C
10.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
10.2: 71 percent / pyridine / 20 °C
11.1: periodic acid / methyl acetate / 20 °C
11.2: camphor sulfonic acid / methanol / 20 °C
12.1: aq. NH3 / methanol / 0 °C
13.1: 2,6-lutidine / CH2Cl2 / 0 °C
14.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
15.1: HgCl2; Et3N / dimethylformamide / 20 °C
16.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
C25H36Cl3NO12Si
794568-32-4

C25H36Cl3NO12Si

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 3 steps
1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
2: HgCl2; Et3N / dimethylformamide / 20 °C
3: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
Acetic acid (1R,3S,5S,6S,7R,8R,9S,10S)-3,6,9-triacetoxy-9-acetoxymethyl-8-dimethoxymethyl-7-(2,2,2-trichloro-acetylamino)-2,4-dioxa-tricyclo[3.3.1.13,7]dec-10-yl ester
794568-30-2

Acetic acid (1R,3S,5S,6S,7R,8R,9S,10S)-3,6,9-triacetoxy-9-acetoxymethyl-8-dimethoxymethyl-7-(2,2,2-trichloro-acetylamino)-2,4-dioxa-tricyclo[3.3.1.13,7]dec-10-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 5 steps
1: aq. NH3 / methanol / 0 °C
2: 2,6-lutidine / CH2Cl2 / 0 °C
3: diisobutylaluminum hydride / CH2Cl2 / -40 °C
4: HgCl2; Et3N / dimethylformamide / 20 °C
5: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1R,2S,5R,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-hydroxymethyl-5,6-bis-triethylsilanyloxy-1-vinyl-cyclohex-3-enyl]-acetamide
794568-19-7

2,2,2-Trichloro-N-[(1R,2S,5R,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-hydroxymethyl-5,6-bis-triethylsilanyloxy-1-vinyl-cyclohex-3-enyl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 15 steps
1.1: 2,6-lutidine / CH2Cl2 / 0 °C
1.2: 83 percent / m-chloroperbenzoic acid; Na2HPO4 / CH2Cl2 / 20 °C
2.1: 90 percent / O3; Et3N / CH2Cl2 / -78 °C
3.1: 70 percent / EtMgBr / tetrahydrofuran / 0 °C
4.1: 4-dimethylaminopyridine / pyridine / 20 °C
4.2: 91 percent / tetrabutylammonium fluoride / tetrahydrofuran / -10 °C
5.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
6.1: H2O2; NaHCO3 / methanol / 20 °C
7.1: 2,6-lutidine / CH2Cl2 / -40 °C
8.1: pyridine / 20 °C
9.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
9.2: 71 percent / pyridine / 20 °C
10.1: periodic acid / methyl acetate / 20 °C
10.2: camphor sulfonic acid / methanol / 20 °C
11.1: aq. NH3 / methanol / 0 °C
12.1: 2,6-lutidine / CH2Cl2 / 0 °C
13.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
14.1: HgCl2; Et3N / dimethylformamide / 20 °C
15.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
Acetic acid (1R,3S,5S,6S,7R,8S,9S,10S)-3,6,9-triacetoxy-9-acetoxymethyl-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-7-(2,2,2-trichloro-acetylamino)-2,4-dioxa-tricyclo[3.3.1.13,7]dec-10-yl ester
794568-29-9

Acetic acid (1R,3S,5S,6S,7R,8S,9S,10S)-3,6,9-triacetoxy-9-acetoxymethyl-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-7-(2,2,2-trichloro-acetylamino)-2,4-dioxa-tricyclo[3.3.1.13,7]dec-10-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 6 steps
1.1: periodic acid / methyl acetate / 20 °C
1.2: camphor sulfonic acid / methanol / 20 °C
2.1: aq. NH3 / methanol / 0 °C
3.1: 2,6-lutidine / CH2Cl2 / 0 °C
4.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
5.1: HgCl2; Et3N / dimethylformamide / 20 °C
6.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1R,4S,5S,6S,7S,8S,9S)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,8-dihydroxy-8-hydroxymethyl-3-oxo-6,7-bis-triethylsilanyloxy-2-oxa-bicyclo[3.3.1]non-5-yl]-acetamide

2,2,2-Trichloro-N-[(1R,4S,5S,6S,7S,8S,9S)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,8-dihydroxy-8-hydroxymethyl-3-oxo-6,7-bis-triethylsilanyloxy-2-oxa-bicyclo[3.3.1]non-5-yl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 9 steps
1.1: 2,6-lutidine / CH2Cl2 / -40 °C
2.1: pyridine / 20 °C
3.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
3.2: 71 percent / pyridine / 20 °C
4.1: periodic acid / methyl acetate / 20 °C
4.2: camphor sulfonic acid / methanol / 20 °C
5.1: aq. NH3 / methanol / 0 °C
6.1: 2,6-lutidine / CH2Cl2 / 0 °C
7.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
8.1: HgCl2; Et3N / dimethylformamide / 20 °C
9.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1S,2S,3R,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-formyl-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-acetamide
794568-21-1

2,2,2-Trichloro-N-[(1S,2S,3R,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-formyl-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 13 steps
1.1: 70 percent / EtMgBr / tetrahydrofuran / 0 °C
2.1: 4-dimethylaminopyridine / pyridine / 20 °C
2.2: 91 percent / tetrabutylammonium fluoride / tetrahydrofuran / -10 °C
3.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
4.1: H2O2; NaHCO3 / methanol / 20 °C
5.1: 2,6-lutidine / CH2Cl2 / -40 °C
6.1: pyridine / 20 °C
7.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
7.2: 71 percent / pyridine / 20 °C
8.1: periodic acid / methyl acetate / 20 °C
8.2: camphor sulfonic acid / methanol / 20 °C
9.1: aq. NH3 / methanol / 0 °C
10.1: 2,6-lutidine / CH2Cl2 / 0 °C
11.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
12.1: HgCl2; Et3N / dimethylformamide / 20 °C
13.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1S,2S,3R,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-3-vinyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-acetamide
947178-10-1

2,2,2-Trichloro-N-[(1S,2S,3R,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-3-vinyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 14 steps
1.1: 90 percent / O3; Et3N / CH2Cl2 / -78 °C
2.1: 70 percent / EtMgBr / tetrahydrofuran / 0 °C
3.1: 4-dimethylaminopyridine / pyridine / 20 °C
3.2: 91 percent / tetrabutylammonium fluoride / tetrahydrofuran / -10 °C
4.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
5.1: H2O2; NaHCO3 / methanol / 20 °C
6.1: 2,6-lutidine / CH2Cl2 / -40 °C
7.1: pyridine / 20 °C
8.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
8.2: 71 percent / pyridine / 20 °C
9.1: periodic acid / methyl acetate / 20 °C
9.2: camphor sulfonic acid / methanol / 20 °C
10.1: aq. NH3 / methanol / 0 °C
11.1: 2,6-lutidine / CH2Cl2 / 0 °C
12.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
13.1: HgCl2; Et3N / dimethylformamide / 20 °C
14.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
Acetic acid (R)-1-[(1S,2S,3S,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-(2,2,2-trichloro-acetylamino)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-prop-2-ynyl ester
794568-23-3

Acetic acid (R)-1-[(1S,2S,3S,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-(2,2,2-trichloro-acetylamino)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-prop-2-ynyl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 11 steps
1.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
2.1: H2O2; NaHCO3 / methanol / 20 °C
3.1: 2,6-lutidine / CH2Cl2 / -40 °C
4.1: pyridine / 20 °C
5.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
5.2: 71 percent / pyridine / 20 °C
6.1: periodic acid / methyl acetate / 20 °C
6.2: camphor sulfonic acid / methanol / 20 °C
7.1: aq. NH3 / methanol / 0 °C
8.1: 2,6-lutidine / CH2Cl2 / 0 °C
9.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
10.1: HgCl2; Et3N / dimethylformamide / 20 °C
11.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1R,4S,5S,6S,7S,8S,9S)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,8-dihydroxy-3-oxo-6,7-bis-triethylsilanyloxy-8-triethylsilanyloxymethyl-2-oxa-bicyclo[3.3.1]non-5-yl]-acetamide
794568-26-6

2,2,2-Trichloro-N-[(1R,4S,5S,6S,7S,8S,9S)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4,8-dihydroxy-3-oxo-6,7-bis-triethylsilanyloxy-8-triethylsilanyloxymethyl-2-oxa-bicyclo[3.3.1]non-5-yl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 8 steps
1.1: pyridine / 20 °C
2.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
2.2: 71 percent / pyridine / 20 °C
3.1: periodic acid / methyl acetate / 20 °C
3.2: camphor sulfonic acid / methanol / 20 °C
4.1: aq. NH3 / methanol / 0 °C
5.1: 2,6-lutidine / CH2Cl2 / 0 °C
6.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
7.1: HgCl2; Et3N / dimethylformamide / 20 °C
8.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
Acetic acid (1R,4S,5S,6S,7S,8S,9S)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-8-hydroxy-3-oxo-5-(2,2,2-trichloro-acetylamino)-6,7-bis-triethylsilanyloxy-8-triethylsilanyloxymethyl-2-oxa-bicyclo[3.3.1]non-4-yl ester
794568-28-8

Acetic acid (1R,4S,5S,6S,7S,8S,9S)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-8-hydroxy-3-oxo-5-(2,2,2-trichloro-acetylamino)-6,7-bis-triethylsilanyloxy-8-triethylsilanyloxymethyl-2-oxa-bicyclo[3.3.1]non-4-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 7 steps
1.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
1.2: 71 percent / pyridine / 20 °C
2.1: periodic acid / methyl acetate / 20 °C
2.2: camphor sulfonic acid / methanol / 20 °C
3.1: aq. NH3 / methanol / 0 °C
4.1: 2,6-lutidine / CH2Cl2 / 0 °C
5.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
6.1: HgCl2; Et3N / dimethylformamide / 20 °C
7.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1S,2S,3S,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-((R)-1-hydroxy-3-trimethylsilanyl-prop-2-ynyl)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-acetamide
794568-22-2

2,2,2-Trichloro-N-[(1S,2S,3S,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-((R)-1-hydroxy-3-trimethylsilanyl-prop-2-ynyl)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 12 steps
1.1: 4-dimethylaminopyridine / pyridine / 20 °C
1.2: 91 percent / tetrabutylammonium fluoride / tetrahydrofuran / -10 °C
2.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
3.1: H2O2; NaHCO3 / methanol / 20 °C
4.1: 2,6-lutidine / CH2Cl2 / -40 °C
5.1: pyridine / 20 °C
6.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
6.2: 71 percent / pyridine / 20 °C
7.1: periodic acid / methyl acetate / 20 °C
7.2: camphor sulfonic acid / methanol / 20 °C
8.1: aq. NH3 / methanol / 0 °C
9.1: 2,6-lutidine / CH2Cl2 / 0 °C
10.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
11.1: HgCl2; Et3N / dimethylformamide / 20 °C
12.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
(S)-3-Acetoxy-3-[(1S,2S,3S,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-(2,2,2-trichloro-acetylamino)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-2-oxo-propionic acid
794568-24-4

(S)-3-Acetoxy-3-[(1S,2S,3S,4S,5S,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-(2,2,2-trichloro-acetylamino)-4,5-bis-triethylsilanyloxy-6-triethylsilanyloxymethyl-7-oxa-bicyclo[4.1.0]hept-3-yl]-2-oxo-propionic acid

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 10 steps
1.1: H2O2; NaHCO3 / methanol / 20 °C
2.1: 2,6-lutidine / CH2Cl2 / -40 °C
3.1: pyridine / 20 °C
4.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
4.2: 71 percent / pyridine / 20 °C
5.1: periodic acid / methyl acetate / 20 °C
5.2: camphor sulfonic acid / methanol / 20 °C
6.1: aq. NH3 / methanol / 0 °C
7.1: 2,6-lutidine / CH2Cl2 / 0 °C
8.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
9.1: HgCl2; Et3N / dimethylformamide / 20 °C
10.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
2,2,2-Trichloro-N-[(1R,2S,5R,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5,6-dihydroxy-4-methyl-1-vinyl-cyclohex-3-enyl]-acetamide
444680-80-2

2,2,2-Trichloro-N-[(1R,2S,5R,6S)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5,6-dihydroxy-4-methyl-1-vinyl-cyclohex-3-enyl]-acetamide

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 17 steps
1.1: 86 percent / pyridine / acetonitrile / 20 °C
2.1: selenium dioxide; pyridine N-oxide / dioxane / Heating
2.2: 48 percent / NaBH4; CeCl3*7H2O / methanol / 0 °C
3.1: 2,6-lutidine / CH2Cl2 / 0 °C
3.2: 83 percent / m-chloroperbenzoic acid; Na2HPO4 / CH2Cl2 / 20 °C
4.1: 90 percent / O3; Et3N / CH2Cl2 / -78 °C
5.1: 70 percent / EtMgBr / tetrahydrofuran / 0 °C
6.1: 4-dimethylaminopyridine / pyridine / 20 °C
6.2: 91 percent / tetrabutylammonium fluoride / tetrahydrofuran / -10 °C
7.1: KMnO4; NaIO4; NaHCO3 / 2-methyl-propan-2-ol; H2O / 50 °C
8.1: H2O2; NaHCO3 / methanol / 20 °C
9.1: 2,6-lutidine / CH2Cl2 / -40 °C
10.1: pyridine / 20 °C
11.1: tetrabutylammonium fluoride / acetonitrile / 0 °C
11.2: 71 percent / pyridine / 20 °C
12.1: periodic acid / methyl acetate / 20 °C
12.2: camphor sulfonic acid / methanol / 20 °C
13.1: aq. NH3 / methanol / 0 °C
14.1: 2,6-lutidine / CH2Cl2 / 0 °C
15.1: diisobutylaluminum hydride / CH2Cl2 / -40 °C
16.1: HgCl2; Et3N / dimethylformamide / 20 °C
17.1: 36 percent / trifluoroacetic acid / H2O / 20 °C
View Scheme
4-O-methyltetrodotoxin

4-O-methyltetrodotoxin

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 2 steps
1: 15 percent / trifluoroacetic acid; D2O / 96 h
2: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
[(2R,5S,6R)-2-Benzyloxymethoxy-4-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-hydroxy-cyclohex-3-en-(E)-ylidene]-acetaldehyde
588693-73-6

[(2R,5S,6R)-2-Benzyloxymethoxy-4-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-hydroxy-cyclohex-3-en-(E)-ylidene]-acetaldehyde

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 34 steps
1.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
2.1: 1.60 g / benzene; methanol / 1 h / 20 °C
3.1: CH2Cl2 / 0.25 h / 0 °C
4.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
5.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
6.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
7.1: pyridine / 10 h / 50 °C
8.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
9.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
10.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
11.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
12.1: Ac2O; DMSO / 2 h / 20 °C
13.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
14.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
15.1: 89 percent / TFA / methanol / 3 h / 20 °C
16.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
17.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
18.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
19.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
20.1: NaBH4 / methanol / 0.25 h / -78 °C
21.1: Et3N; MeOH / 28.8 h / 15 °C
22.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
22.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
23.1: Pd(OH)2/C / methanol / 12 h / 20 °C
24.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
25.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
26.1: CAN / acetonitrile; H2O / 2 h / 85 °C
27.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
28.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
29.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
30.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
31.1: HCl; dioxane / 24 h
32.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
33.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
34.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 35 steps
1.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
2.1: 1.60 g / benzene; methanol / 1 h / 20 °C
3.1: CH2Cl2 / 0.25 h / 0 °C
4.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
5.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
6.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
7.1: pyridine / 10 h / 50 °C
8.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
9.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
10.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
11.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
12.1: Ac2O; DMSO / 2 h / 20 °C
13.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
14.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
15.1: 89 percent / TFA / methanol / 3 h / 20 °C
16.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
17.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
18.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
19.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
20.1: NaBH4 / methanol / 0.25 h / -78 °C
21.1: Et3N; MeOH / 28.8 h / 15 °C
22.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
22.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
23.1: Pd(OH)2/C / methanol / 12 h / 20 °C
24.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
25.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
26.1: CAN / acetonitrile; H2O / 2 h / 85 °C
27.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
28.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
29.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
30.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
31.1: HCl; dioxane / 24 h
32.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
33.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
34.1: 15 percent / trifluoroacetic acid; D2O / 96 h
35.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 34 steps
1.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
2.1: 1.60 g / benzene; methanol / 1 h / 20 °C
3.1: CH2Cl2 / 0.25 h / 0 °C
4.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
5.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
6.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
7.1: pyridine / 10 h / 50 °C
8.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
9.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
10.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
11.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
12.1: Ac2O; DMSO / 2 h / 20 °C
13.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
14.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
15.1: 89 percent / TFA / methanol / 3 h / 20 °C
16.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
17.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
18.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
19.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
20.1: NaBH4 / methanol / 0.25 h / -78 °C
21.1: Et3N; MeOH / 28.8 h / 15 °C
22.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
22.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
23.1: Pd(OH)2/C / methanol / 12 h / 20 °C
24.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
25.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
26.1: CAN / acetonitrile; H2O / 2 h / 85 °C
27.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
28.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
29.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
30.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
31.1: HCl; dioxane / 24 h
32.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
33.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
34.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
(1S,4R,6R)-4-Benzyloxymethoxy-2-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-[2-hydroxy-eth-(E)-ylidene]-cyclohex-2-enol
588693-71-4

(1S,4R,6R)-4-Benzyloxymethoxy-2-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-[2-hydroxy-eth-(E)-ylidene]-cyclohex-2-enol

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 35 steps
1.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
2.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
3.1: 1.60 g / benzene; methanol / 1 h / 20 °C
4.1: CH2Cl2 / 0.25 h / 0 °C
5.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
6.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
7.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
8.1: pyridine / 10 h / 50 °C
9.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
10.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
11.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
12.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
13.1: Ac2O; DMSO / 2 h / 20 °C
14.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
15.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
16.1: 89 percent / TFA / methanol / 3 h / 20 °C
17.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
18.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
19.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
20.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
21.1: NaBH4 / methanol / 0.25 h / -78 °C
22.1: Et3N; MeOH / 28.8 h / 15 °C
23.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
23.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
24.1: Pd(OH)2/C / methanol / 12 h / 20 °C
25.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
26.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
27.1: CAN / acetonitrile; H2O / 2 h / 85 °C
28.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
29.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
30.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
31.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
32.1: HCl; dioxane / 24 h
33.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
34.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
35.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 36 steps
1.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
2.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
3.1: 1.60 g / benzene; methanol / 1 h / 20 °C
4.1: CH2Cl2 / 0.25 h / 0 °C
5.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
6.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
7.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
8.1: pyridine / 10 h / 50 °C
9.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
10.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
11.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
12.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
13.1: Ac2O; DMSO / 2 h / 20 °C
14.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
15.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
16.1: 89 percent / TFA / methanol / 3 h / 20 °C
17.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
18.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
19.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
20.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
21.1: NaBH4 / methanol / 0.25 h / -78 °C
22.1: Et3N; MeOH / 28.8 h / 15 °C
23.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
23.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
24.1: Pd(OH)2/C / methanol / 12 h / 20 °C
25.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
26.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
27.1: CAN / acetonitrile; H2O / 2 h / 85 °C
28.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
29.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
30.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
31.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
32.1: HCl; dioxane / 24 h
33.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
34.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
35.1: 15 percent / trifluoroacetic acid; D2O / 96 h
36.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 35 steps
1.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
2.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
3.1: 1.60 g / benzene; methanol / 1 h / 20 °C
4.1: CH2Cl2 / 0.25 h / 0 °C
5.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
6.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
7.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
8.1: pyridine / 10 h / 50 °C
9.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
10.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
11.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
12.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
13.1: Ac2O; DMSO / 2 h / 20 °C
14.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
15.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
16.1: 89 percent / TFA / methanol / 3 h / 20 °C
17.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
18.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
19.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
20.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
21.1: NaBH4 / methanol / 0.25 h / -78 °C
22.1: Et3N; MeOH / 28.8 h / 15 °C
23.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
23.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
24.1: Pd(OH)2/C / methanol / 12 h / 20 °C
25.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
26.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
27.1: CAN / acetonitrile; H2O / 2 h / 85 °C
28.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
29.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
30.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
31.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
32.1: HCl; dioxane / 24 h
33.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
34.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
35.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
[(2R,5S,6R)-2-Benzyloxymethoxy-4-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-hydroxy-cyclohex-3-en-(E)-ylidene]-acetic acid methyl ester
588693-75-8

[(2R,5S,6R)-2-Benzyloxymethoxy-4-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-hydroxy-cyclohex-3-en-(E)-ylidene]-acetic acid methyl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 32 steps
1.1: CH2Cl2 / 0.25 h / 0 °C
2.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
3.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
4.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
5.1: pyridine / 10 h / 50 °C
6.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
7.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
8.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
9.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
10.1: Ac2O; DMSO / 2 h / 20 °C
11.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
12.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
13.1: 89 percent / TFA / methanol / 3 h / 20 °C
14.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
15.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
16.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
17.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
18.1: NaBH4 / methanol / 0.25 h / -78 °C
19.1: Et3N; MeOH / 28.8 h / 15 °C
20.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
20.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
21.1: Pd(OH)2/C / methanol / 12 h / 20 °C
22.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
23.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
24.1: CAN / acetonitrile; H2O / 2 h / 85 °C
25.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
26.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
27.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
28.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
29.1: HCl; dioxane / 24 h
30.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
31.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
32.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 33 steps
1.1: CH2Cl2 / 0.25 h / 0 °C
2.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
3.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
4.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
5.1: pyridine / 10 h / 50 °C
6.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
7.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
8.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
9.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
10.1: Ac2O; DMSO / 2 h / 20 °C
11.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
12.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
13.1: 89 percent / TFA / methanol / 3 h / 20 °C
14.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
15.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
16.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
17.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
18.1: NaBH4 / methanol / 0.25 h / -78 °C
19.1: Et3N; MeOH / 28.8 h / 15 °C
20.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
20.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
21.1: Pd(OH)2/C / methanol / 12 h / 20 °C
22.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
23.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
24.1: CAN / acetonitrile; H2O / 2 h / 85 °C
25.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
26.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
27.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
28.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
29.1: HCl; dioxane / 24 h
30.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
31.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
32.1: 15 percent / trifluoroacetic acid; D2O / 96 h
33.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 32 steps
1.1: CH2Cl2 / 0.25 h / 0 °C
2.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
3.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
4.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
5.1: pyridine / 10 h / 50 °C
6.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
7.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
8.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
9.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
10.1: Ac2O; DMSO / 2 h / 20 °C
11.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
12.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
13.1: 89 percent / TFA / methanol / 3 h / 20 °C
14.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
15.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
16.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
17.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
18.1: NaBH4 / methanol / 0.25 h / -78 °C
19.1: Et3N; MeOH / 28.8 h / 15 °C
20.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
20.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
21.1: Pd(OH)2/C / methanol / 12 h / 20 °C
22.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
23.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
24.1: CAN / acetonitrile; H2O / 2 h / 85 °C
25.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
26.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
27.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
28.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
29.1: HCl; dioxane / 24 h
30.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
31.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
32.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
[(2R,5S,6R)-2-Benzyloxymethoxy-4-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-hydroxy-cyclohex-3-en-(E)-ylidene]-acetic acid

[(2R,5S,6R)-2-Benzyloxymethoxy-4-(tert-butyl-diphenyl-silanyloxymethyl)-6-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-hydroxy-cyclohex-3-en-(E)-ylidene]-acetic acid

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 33 steps
1.1: 1.60 g / benzene; methanol / 1 h / 20 °C
2.1: CH2Cl2 / 0.25 h / 0 °C
3.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
4.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
5.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
6.1: pyridine / 10 h / 50 °C
7.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
8.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
9.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
10.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
11.1: Ac2O; DMSO / 2 h / 20 °C
12.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
13.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
14.1: 89 percent / TFA / methanol / 3 h / 20 °C
15.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
16.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
17.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
18.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
19.1: NaBH4 / methanol / 0.25 h / -78 °C
20.1: Et3N; MeOH / 28.8 h / 15 °C
21.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
21.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
22.1: Pd(OH)2/C / methanol / 12 h / 20 °C
23.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
24.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
25.1: CAN / acetonitrile; H2O / 2 h / 85 °C
26.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
27.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
28.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
29.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
30.1: HCl; dioxane / 24 h
31.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
32.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
33.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 34 steps
1.1: 1.60 g / benzene; methanol / 1 h / 20 °C
2.1: CH2Cl2 / 0.25 h / 0 °C
3.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
4.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
5.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
6.1: pyridine / 10 h / 50 °C
7.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
8.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
9.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
10.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
11.1: Ac2O; DMSO / 2 h / 20 °C
12.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
13.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
14.1: 89 percent / TFA / methanol / 3 h / 20 °C
15.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
16.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
17.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
18.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
19.1: NaBH4 / methanol / 0.25 h / -78 °C
20.1: Et3N; MeOH / 28.8 h / 15 °C
21.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
21.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
22.1: Pd(OH)2/C / methanol / 12 h / 20 °C
23.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
24.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
25.1: CAN / acetonitrile; H2O / 2 h / 85 °C
26.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
27.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
28.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
29.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
30.1: HCl; dioxane / 24 h
31.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
32.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
33.1: 15 percent / trifluoroacetic acid; D2O / 96 h
34.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 33 steps
1.1: 1.60 g / benzene; methanol / 1 h / 20 °C
2.1: CH2Cl2 / 0.25 h / 0 °C
3.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
4.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
5.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
6.1: pyridine / 10 h / 50 °C
7.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
8.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
9.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
10.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
11.1: Ac2O; DMSO / 2 h / 20 °C
12.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
13.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
14.1: 89 percent / TFA / methanol / 3 h / 20 °C
15.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
16.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
17.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
18.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
19.1: NaBH4 / methanol / 0.25 h / -78 °C
20.1: Et3N; MeOH / 28.8 h / 15 °C
21.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
21.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
22.1: Pd(OH)2/C / methanol / 12 h / 20 °C
23.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
24.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
25.1: CAN / acetonitrile; H2O / 2 h / 85 °C
26.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
27.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
28.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
29.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
30.1: HCl; dioxane / 24 h
31.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
32.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
33.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Benzoic acid (1S,2R,3S,4R,5S,6R)-2-acetoxy-5-benzyloxymethoxy-4-tert-butoxycarbonylamino-3-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-(2-oxo-ethyl)-7-oxa-bicyclo[4.1.0]hept-1-ylmethyl ester
588693-98-5

Benzoic acid (1S,2R,3S,4R,5S,6R)-2-acetoxy-5-benzyloxymethoxy-4-tert-butoxycarbonylamino-3-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-(2-oxo-ethyl)-7-oxa-bicyclo[4.1.0]hept-1-ylmethyl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 18 steps
1.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
2.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
3.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
4.1: NaBH4 / methanol / 0.25 h / -78 °C
5.1: Et3N; MeOH / 28.8 h / 15 °C
6.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
6.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
7.1: Pd(OH)2/C / methanol / 12 h / 20 °C
8.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
9.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
10.1: CAN / acetonitrile; H2O / 2 h / 85 °C
11.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
12.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
13.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
14.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
15.1: HCl; dioxane / 24 h
16.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
17.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
18.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 19 steps
1.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
2.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
3.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
4.1: NaBH4 / methanol / 0.25 h / -78 °C
5.1: Et3N; MeOH / 28.8 h / 15 °C
6.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
6.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
7.1: Pd(OH)2/C / methanol / 12 h / 20 °C
8.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
9.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
10.1: CAN / acetonitrile; H2O / 2 h / 85 °C
11.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
12.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
13.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
14.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
15.1: HCl; dioxane / 24 h
16.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
17.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
18.1: 15 percent / trifluoroacetic acid; D2O / 96 h
19.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 18 steps
1.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
2.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
3.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
4.1: NaBH4 / methanol / 0.25 h / -78 °C
5.1: Et3N; MeOH / 28.8 h / 15 °C
6.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
6.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
7.1: Pd(OH)2/C / methanol / 12 h / 20 °C
8.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
9.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
10.1: CAN / acetonitrile; H2O / 2 h / 85 °C
11.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
12.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
13.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
14.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
15.1: HCl; dioxane / 24 h
16.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
17.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
18.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Benzoic acid (1S,5R,8S,8aR)-5-benzyloxymethoxy-7-(tert-butyl-diphenyl-silanyloxymethyl)-1-hydroxymethyl-3-methoxy-3,5,8,8a-tetrahydro-1H-isochromen-8-yl ester

Benzoic acid (1S,5R,8S,8aR)-5-benzyloxymethoxy-7-(tert-butyl-diphenyl-silanyloxymethyl)-1-hydroxymethyl-3-methoxy-3,5,8,8a-tetrahydro-1H-isochromen-8-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 41 steps
1.1: 12.80 g / DMAP / pyridine / 3 h / 20 °C
2.1: 1.60 g / aq. PPTS; HgO / acetone / 7 h / 55 °C
3.1: Mg(OEt)2 / methanol; ethyl acetate / 1 h / 20 °C
4.1: NaBH4 / methanol / 0.25 h / 20 °C
5.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
5.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
6.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
7.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
8.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
9.1: 1.60 g / benzene; methanol / 1 h / 20 °C
10.1: CH2Cl2 / 0.25 h / 0 °C
11.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
12.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
13.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
14.1: pyridine / 10 h / 50 °C
15.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
16.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
17.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
18.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
19.1: Ac2O; DMSO / 2 h / 20 °C
20.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
21.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
22.1: 89 percent / TFA / methanol / 3 h / 20 °C
23.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
24.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
25.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
26.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
27.1: NaBH4 / methanol / 0.25 h / -78 °C
28.1: Et3N; MeOH / 28.8 h / 15 °C
29.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
29.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
30.1: Pd(OH)2/C / methanol / 12 h / 20 °C
31.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
32.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
33.1: CAN / acetonitrile; H2O / 2 h / 85 °C
34.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
35.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
36.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
37.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
38.1: HCl; dioxane / 24 h
39.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
40.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
41.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 42 steps
1.1: 12.80 g / DMAP / pyridine / 3 h / 20 °C
2.1: 1.60 g / aq. PPTS; HgO / acetone / 7 h / 55 °C
3.1: Mg(OEt)2 / methanol; ethyl acetate / 1 h / 20 °C
4.1: NaBH4 / methanol / 0.25 h / 20 °C
5.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
5.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
6.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
7.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
8.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
9.1: 1.60 g / benzene; methanol / 1 h / 20 °C
10.1: CH2Cl2 / 0.25 h / 0 °C
11.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
12.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
13.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
14.1: pyridine / 10 h / 50 °C
15.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
16.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
17.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
18.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
19.1: Ac2O; DMSO / 2 h / 20 °C
20.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
21.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
22.1: 89 percent / TFA / methanol / 3 h / 20 °C
23.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
24.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
25.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
26.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
27.1: NaBH4 / methanol / 0.25 h / -78 °C
28.1: Et3N; MeOH / 28.8 h / 15 °C
29.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
29.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
30.1: Pd(OH)2/C / methanol / 12 h / 20 °C
31.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
32.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
33.1: CAN / acetonitrile; H2O / 2 h / 85 °C
34.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
35.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
36.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
37.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
38.1: HCl; dioxane / 24 h
39.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
40.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
41.1: 15 percent / trifluoroacetic acid; D2O / 96 h
42.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 41 steps
1.1: 12.80 g / DMAP / pyridine / 3 h / 20 °C
2.1: 1.60 g / aq. PPTS; HgO / acetone / 7 h / 55 °C
3.1: Mg(OEt)2 / methanol; ethyl acetate / 1 h / 20 °C
4.1: NaBH4 / methanol / 0.25 h / 20 °C
5.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
5.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
6.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
7.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
8.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
9.1: 1.60 g / benzene; methanol / 1 h / 20 °C
10.1: CH2Cl2 / 0.25 h / 0 °C
11.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
12.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
13.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
14.1: pyridine / 10 h / 50 °C
15.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
16.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
17.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
18.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
19.1: Ac2O; DMSO / 2 h / 20 °C
20.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
21.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
22.1: 89 percent / TFA / methanol / 3 h / 20 °C
23.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
24.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
25.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
26.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
27.1: NaBH4 / methanol / 0.25 h / -78 °C
28.1: Et3N; MeOH / 28.8 h / 15 °C
29.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
29.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
30.1: Pd(OH)2/C / methanol / 12 h / 20 °C
31.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
32.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
33.1: CAN / acetonitrile; H2O / 2 h / 85 °C
34.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
35.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
36.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
37.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
38.1: HCl; dioxane / 24 h
39.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
40.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
41.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
benzoic acid 1-(tert-butyl-dimethyl-silanyloxymethyl)-7-(tert-butyl-diphenyl-silanyloxymethyl)-5-hydroxy-3-methoxy-3,5,8,8a-tetrahydro-1H-isochromen-8-yl ester
588693-55-4

benzoic acid 1-(tert-butyl-dimethyl-silanyloxymethyl)-7-(tert-butyl-diphenyl-silanyloxymethyl)-5-hydroxy-3-methoxy-3,5,8,8a-tetrahydro-1H-isochromen-8-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 43 steps
1.1: i-Pr2NEt; DMAP / 1,2-dichloro-ethane / 4 h / 60 °C
2.1: (+/-)-CSA; MeOH / 1 h / 20 °C
3.1: 12.80 g / DMAP / pyridine / 3 h / 20 °C
4.1: 1.60 g / aq. PPTS; HgO / acetone / 7 h / 55 °C
5.1: Mg(OEt)2 / methanol; ethyl acetate / 1 h / 20 °C
6.1: NaBH4 / methanol / 0.25 h / 20 °C
7.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
7.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
8.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
9.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
10.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
11.1: 1.60 g / benzene; methanol / 1 h / 20 °C
12.1: CH2Cl2 / 0.25 h / 0 °C
13.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
14.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
15.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
16.1: pyridine / 10 h / 50 °C
17.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
18.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
19.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
20.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
21.1: Ac2O; DMSO / 2 h / 20 °C
22.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
23.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
24.1: 89 percent / TFA / methanol / 3 h / 20 °C
25.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
26.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
27.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
28.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
29.1: NaBH4 / methanol / 0.25 h / -78 °C
30.1: Et3N; MeOH / 28.8 h / 15 °C
31.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
31.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
32.1: Pd(OH)2/C / methanol / 12 h / 20 °C
33.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
34.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
35.1: CAN / acetonitrile; H2O / 2 h / 85 °C
36.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
37.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
38.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
39.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
40.1: HCl; dioxane / 24 h
41.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
42.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
43.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 44 steps
1.1: i-Pr2NEt; DMAP / 1,2-dichloro-ethane / 4 h / 60 °C
2.1: (+/-)-CSA; MeOH / 1 h / 20 °C
3.1: 12.80 g / DMAP / pyridine / 3 h / 20 °C
4.1: 1.60 g / aq. PPTS; HgO / acetone / 7 h / 55 °C
5.1: Mg(OEt)2 / methanol; ethyl acetate / 1 h / 20 °C
6.1: NaBH4 / methanol / 0.25 h / 20 °C
7.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
7.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
8.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
9.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
10.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
11.1: 1.60 g / benzene; methanol / 1 h / 20 °C
12.1: CH2Cl2 / 0.25 h / 0 °C
13.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
14.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
15.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
16.1: pyridine / 10 h / 50 °C
17.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
18.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
19.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
20.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
21.1: Ac2O; DMSO / 2 h / 20 °C
22.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
23.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
24.1: 89 percent / TFA / methanol / 3 h / 20 °C
25.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
26.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
27.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
28.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
29.1: NaBH4 / methanol / 0.25 h / -78 °C
30.1: Et3N; MeOH / 28.8 h / 15 °C
31.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
31.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
32.1: Pd(OH)2/C / methanol / 12 h / 20 °C
33.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
34.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
35.1: CAN / acetonitrile; H2O / 2 h / 85 °C
36.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
37.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
38.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
39.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
40.1: HCl; dioxane / 24 h
41.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
42.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
43.1: 15 percent / trifluoroacetic acid; D2O / 96 h
44.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 43 steps
1.1: i-Pr2NEt; DMAP / 1,2-dichloro-ethane / 4 h / 60 °C
2.1: (+/-)-CSA; MeOH / 1 h / 20 °C
3.1: 12.80 g / DMAP / pyridine / 3 h / 20 °C
4.1: 1.60 g / aq. PPTS; HgO / acetone / 7 h / 55 °C
5.1: Mg(OEt)2 / methanol; ethyl acetate / 1 h / 20 °C
6.1: NaBH4 / methanol / 0.25 h / 20 °C
7.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
7.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
8.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
9.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
10.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
11.1: 1.60 g / benzene; methanol / 1 h / 20 °C
12.1: CH2Cl2 / 0.25 h / 0 °C
13.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
14.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
15.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
16.1: pyridine / 10 h / 50 °C
17.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
18.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
19.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
20.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
21.1: Ac2O; DMSO / 2 h / 20 °C
22.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
23.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
24.1: 89 percent / TFA / methanol / 3 h / 20 °C
25.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
26.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
27.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
28.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
29.1: NaBH4 / methanol / 0.25 h / -78 °C
30.1: Et3N; MeOH / 28.8 h / 15 °C
31.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
31.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
32.1: Pd(OH)2/C / methanol / 12 h / 20 °C
33.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
34.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
35.1: CAN / acetonitrile; H2O / 2 h / 85 °C
36.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
37.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
38.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
39.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
40.1: HCl; dioxane / 24 h
41.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
42.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
43.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Benzoic acid (1S,5R,8S,8aR)-5-benzyloxymethoxy-7-(tert-butyl-diphenyl-silanyloxymethyl)-3-hydroxy-1-hydroxymethyl-3,5,8,8a-tetrahydro-1H-isochromen-8-yl ester
588693-65-6

Benzoic acid (1S,5R,8S,8aR)-5-benzyloxymethoxy-7-(tert-butyl-diphenyl-silanyloxymethyl)-3-hydroxy-1-hydroxymethyl-3,5,8,8a-tetrahydro-1H-isochromen-8-yl ester

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 38 steps
1.1: NaBH4 / methanol / 0.25 h / 20 °C
2.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
2.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
3.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
4.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
5.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
6.1: 1.60 g / benzene; methanol / 1 h / 20 °C
7.1: CH2Cl2 / 0.25 h / 0 °C
8.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
9.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
10.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
11.1: pyridine / 10 h / 50 °C
12.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
13.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
14.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
15.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
16.1: Ac2O; DMSO / 2 h / 20 °C
17.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
18.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
19.1: 89 percent / TFA / methanol / 3 h / 20 °C
20.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
21.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
22.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
23.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
24.1: NaBH4 / methanol / 0.25 h / -78 °C
25.1: Et3N; MeOH / 28.8 h / 15 °C
26.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
26.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
27.1: Pd(OH)2/C / methanol / 12 h / 20 °C
28.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
29.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
30.1: CAN / acetonitrile; H2O / 2 h / 85 °C
31.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
32.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
33.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
34.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
35.1: HCl; dioxane / 24 h
36.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
37.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
38.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 39 steps
1.1: NaBH4 / methanol / 0.25 h / 20 °C
2.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
2.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
3.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
4.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
5.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
6.1: 1.60 g / benzene; methanol / 1 h / 20 °C
7.1: CH2Cl2 / 0.25 h / 0 °C
8.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
9.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
10.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
11.1: pyridine / 10 h / 50 °C
12.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
13.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
14.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
15.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
16.1: Ac2O; DMSO / 2 h / 20 °C
17.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
18.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
19.1: 89 percent / TFA / methanol / 3 h / 20 °C
20.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
21.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
22.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
23.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
24.1: NaBH4 / methanol / 0.25 h / -78 °C
25.1: Et3N; MeOH / 28.8 h / 15 °C
26.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
26.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
27.1: Pd(OH)2/C / methanol / 12 h / 20 °C
28.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
29.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
30.1: CAN / acetonitrile; H2O / 2 h / 85 °C
31.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
32.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
33.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
34.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
35.1: HCl; dioxane / 24 h
36.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
37.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
38.1: 15 percent / trifluoroacetic acid; D2O / 96 h
39.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 38 steps
1.1: NaBH4 / methanol / 0.25 h / 20 °C
2.1: (+/-)-CSA / acetone / 0.67 h / 20 °C
2.2: 6.88 g / PPTS; MeOH / 0.08 h / 20 °C
3.1: 99 percent / DIBAL-H / CH2Cl2 / 0.25 h / -78 °C
4.1: 94 percent / K2CO3; Bu4NCl; NCS / TEMPO / CH2Cl2; aq. NaHCO3 / 0.5 h / 20 °C
5.1: 2-methyl-2-butene; aq. NaH2PO4; NaClO2 / 2-methyl-propan-2-ol / 1 h / 20 °C
6.1: 1.60 g / benzene; methanol / 1 h / 20 °C
7.1: CH2Cl2 / 0.25 h / 0 °C
8.1: 1.68 g / K2CO3 / methanol / 10 h / 0 °C
9.1: 90 percent / t-BuOK / tetrahydrofuran / 0.5 h / -78 - -15 °C
10.1: LiBH4 / tetrahydrofuran / 3 h / 20 °C
11.1: pyridine / 10 h / 50 °C
12.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
13.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
14.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
15.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
16.1: Ac2O; DMSO / 2 h / 20 °C
17.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
18.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
19.1: 89 percent / TFA / methanol / 3 h / 20 °C
20.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
21.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
22.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
23.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
24.1: NaBH4 / methanol / 0.25 h / -78 °C
25.1: Et3N; MeOH / 28.8 h / 15 °C
26.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
26.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
27.1: Pd(OH)2/C / methanol / 12 h / 20 °C
28.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
29.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
30.1: CAN / acetonitrile; H2O / 2 h / 85 °C
31.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
32.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
33.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
34.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
35.1: HCl; dioxane / 24 h
36.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
37.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
38.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
(1S,5R,6R,9R)-6-Benzyloxymethoxy-8-(tert-butyl-diphenyl-silanyloxymethyl)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-(2-hydroxy-ethyl)-2-oxa-4-aza-bicyclo[3.3.1]non-7-en-3-one

(1S,5R,6R,9R)-6-Benzyloxymethoxy-8-(tert-butyl-diphenyl-silanyloxymethyl)-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-5-(2-hydroxy-ethyl)-2-oxa-4-aza-bicyclo[3.3.1]non-7-en-3-one

tetradotoxin
4368-28-9

tetradotoxin

Conditions
ConditionsYield
Multi-step reaction with 28 steps
1.1: pyridine / 10 h / 50 °C
2.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
3.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
4.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
5.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
6.1: Ac2O; DMSO / 2 h / 20 °C
7.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
8.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
9.1: 89 percent / TFA / methanol / 3 h / 20 °C
10.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
11.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
12.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
13.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
14.1: NaBH4 / methanol / 0.25 h / -78 °C
15.1: Et3N; MeOH / 28.8 h / 15 °C
16.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
16.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
17.1: Pd(OH)2/C / methanol / 12 h / 20 °C
18.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
19.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
20.1: CAN / acetonitrile; H2O / 2 h / 85 °C
21.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
22.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
23.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
24.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
25.1: HCl; dioxane / 24 h
26.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
27.1: 18 percent / Et3N / aq. methanol / 8 h / 20 °C
28.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 29 steps
1.1: pyridine / 10 h / 50 °C
2.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
3.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
4.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
5.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
6.1: Ac2O; DMSO / 2 h / 20 °C
7.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
8.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
9.1: 89 percent / TFA / methanol / 3 h / 20 °C
10.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
11.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
12.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
13.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
14.1: NaBH4 / methanol / 0.25 h / -78 °C
15.1: Et3N; MeOH / 28.8 h / 15 °C
16.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
16.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
17.1: Pd(OH)2/C / methanol / 12 h / 20 °C
18.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
19.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
20.1: CAN / acetonitrile; H2O / 2 h / 85 °C
21.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
22.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
23.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
24.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
25.1: HCl; dioxane / 24 h
26.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
27.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
28.1: 15 percent / trifluoroacetic acid; D2O / 96 h
29.1: 63 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
Multi-step reaction with 28 steps
1.1: pyridine / 10 h / 50 °C
2.1: 2.15 g / Et3N; DMAP / tetrahydrofuran / 48 h / 20 °C
3.1: 85 percent / aq. LiOH / methanol; 1,2-dichloro-ethane / 24 h / 40 °C
4.1: 98 percent / Na2HPO4; m-CPBA / 1,2-dichloro-ethane / 12 h / 20 °C
5.1: 95 percent / Et3N / CH2Cl2 / 0.67 h / -42 °C
6.1: Ac2O; DMSO / 2 h / 20 °C
7.1: 1.04 g / NaBH4 / methanol / 0.25 h / 0 °C
8.1: 100 percent / DMAP / pyridine / 1.5 h / 20 °C
9.1: 89 percent / TFA / methanol / 3 h / 20 °C
10.1: 100 percent / o-iodoxybenzoic acid / dimethylsulfoxide / 3 h / 20 °C
11.1: DBU / 1,2-dichloro-benzene / 0.33 h / 130 °C
12.1: NMO; OsO4 / acetone; H2O / 3 h / 20 °C
13.1: 141 mg / o-iodoxybenzoic acid / dimethylsulfoxide / 0.42 h / 55 °C
14.1: NaBH4 / methanol / 0.25 h / -78 °C
15.1: Et3N; MeOH / 28.8 h / 15 °C
16.1: pyridine; Et3N / CH2Cl2 / 0.5 h / 0 °C
16.2: pyridine; DMAP / CH2Cl2 / 2 h / 20 °C
17.1: Pd(OH)2/C / methanol / 12 h / 20 °C
18.1: 96 mg / DMAP / pyridine / 2 h / 20 °C
19.1: 75 percent / aq. TFA / methanol; H2O / 26.4 h / 20 °C
20.1: CAN / acetonitrile; H2O / 2 h / 85 °C
21.1: 38.5 mg / Et3N; HgCl2 / dimethylformamide / 2 h / 20 °C
22.1: NaIO4 / methanol; H2O / 0.5 h / 20 °C
23.1: 22.9 mg / TFA / methanol / 1.5 h / 20 °C
24.1: aq. HCl / tetrahydrofuran / 24 h / 20 °C
25.1: HCl; dioxane / 24 h
26.1: 11.2 mg / Et3N / pyridine / 12 h / 40 °C
27.1: 67 percent / Et3N / aq. methanol / 8 h / 20 °C
28.1: 66 percent / trifluoroacetic acid; D2O / 96 h
View Scheme
tetradotoxin
4368-28-9

tetradotoxin

acetone
67-64-1

acetone

A

6,11-O-isopropylidene-4,9-anhydrotetrodotoxin hydrochloride

6,11-O-isopropylidene-4,9-anhydrotetrodotoxin hydrochloride

B

6,11-O-isopropylidene-4,9-anhydrotetrodotoxin hydrochloride

6,11-O-isopropylidene-4,9-anhydrotetrodotoxin hydrochloride

Conditions
ConditionsYield
Stage #1: acetone With methanol; acetyl chloride at 20℃; for 0.5h;
Stage #2: tetradotoxin for 26 - 192h; Product distribution / selectivity;
A 22%
B 47%
methanol
67-56-1

methanol

tetradotoxin
4368-28-9

tetradotoxin

acetone
67-64-1

acetone

4-O-methyl-6,11-O-isopropylidene-4,9-anhydrotetrodotoxin hydrochloride

4-O-methyl-6,11-O-isopropylidene-4,9-anhydrotetrodotoxin hydrochloride

Conditions
ConditionsYield
Stage #1: methanol; acetone With acetyl chloride at 20℃; for 0.5h;
Stage #2: tetradotoxin for 16h; Product distribution / selectivity;
45%
acetic anhydride
108-24-7

acetic anhydride

tetradotoxin
4368-28-9

tetradotoxin

(5S)-8t-acetoxy-8c-acetoxymethyl-2-amino-(3at,7at,10bt)-3a,7a,8,9,10,10b-hexahydro-1(3)H-5r,10ac-cyclo-6c,9c-epioxido-[1,4]dioxepino[5,6,7-de]quinazoline-6,10c-diol
13285-84-2

(5S)-8t-acetoxy-8c-acetoxymethyl-2-amino-(3at,7at,10bt)-3a,7a,8,9,10,10b-hexahydro-1(3)H-5r,10ac-cyclo-6c,9c-epioxido-[1,4]dioxepino[5,6,7-de]quinazoline-6,10c-diol

Conditions
ConditionsYield
(i) TsOH, (ii) Py, (iii) aq. NH3; Multistep reaction;
tetradotoxin
4368-28-9

tetradotoxin

4,9-anhydrotetrodotoxin
13072-89-4

4,9-anhydrotetrodotoxin

Conditions
ConditionsYield
(i) Ac2O, TsOH, (ii) Py, (iii) aq. NH3; Multistep reaction;
tetradotoxin
4368-28-9

tetradotoxin

(5R)-2,4c-diamino-12-hydroxymethyl-(4ac)-1(3),4,4a,5,9,10-hexahydro-5r,9c;7t,10at-dimethano-[1,3]dioxocino[6,5-d]pyrimidine-7,10t,11syn,12syn-tetraol
7724-38-1

(5R)-2,4c-diamino-12-hydroxymethyl-(4ac)-1(3),4,4a,5,9,10-hexahydro-5r,9c;7t,10at-dimethano-[1,3]dioxocino[6,5-d]pyrimidine-7,10t,11syn,12syn-tetraol

Conditions
ConditionsYield
(i) Ac2O, TsOH, (ii) Py, (iii) aq. NH3; Multistep reaction;
tetradotoxin
4368-28-9

tetradotoxin

(7S)-2-amino-4c,5t,10t,11anti-tetrahydroxy-(4ac)-1(3),4,4a,5-tetrahydro-7r,10ac-methano-oxocino[4,5-d]pyrimidine-6,9-dione
6548-69-2

(7S)-2-amino-4c,5t,10t,11anti-tetrahydroxy-(4ac)-1(3),4,4a,5-tetrahydro-7r,10ac-methano-oxocino[4,5-d]pyrimidine-6,9-dione

Conditions
ConditionsYield
With sulfuric acid; periodic acid at 0℃;

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