473-03-0

Basic information

• Product Name: 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol
• Synonyms: 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol;ambrein;2-Naphthalenol, 1-[6-(2,2-dimethyl-6-methylenecyclohexyl) -4-methyl-3-hexenyl]decahydro-2,5 ,5,8a-tetramethyl-, [1R-[1α[E(S)],2,4a,8aα]]-;(1R,4aα)-1-[(E)-6-[(S)-2,2-Dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalen-2α-ol;(E)-Ambra-13,18(28)-dien-8-ol;2-Naphthalenol, 1-((3E)-6-((1S)-2,2-dimethyl-6-methylenecyclohexyl)-4-methyl-3-hexenyl)decahydro-2,5,5,8A-tetramethyl-, (1R,2R,4as,8as)-;2-Naphthalenol, 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methyl-3-hexenyl)decahydro-2,5,5,8A-tetramethyl-, (1theta-(1alpha(E(S)),2beta,4abeta,8aalpha))-;2-Naphthalenol, decahydro-1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methyl-3-hexenyl)-2,5,5,8A-tetramethyl-, (1R-(1-alpha(E(S*)),2-beta,4A-beta,8A-alpha))-
• CAS NO: 473-03-0
• Molecular Formula: C₃₀H₅₂O
• Molecular Weight: 428.73328
• EINECS: 207-460-3
• Product Categories: Organics
• Mol File: 473-03-0.mol
• Article Data: 6

Chemical Properties

• Boiling Point: 495.3°Cat760mmHg
• Flash Point: 222°C
• Appearance: /
• Density: 0.94g/cm³
• Vapor Pressure: 6.9E-12mmHg at 25°C
• Refractive Index: 1.511
• CAS DataBase Reference: 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol(CAS DataBase Reference)
• NIST Chemistry Reference: 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol(473-03-0)
• EPA Substance Registry System: 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol(473-03-0)

Safety Data

• Hazardous Substances Data: 473-03-0(Hazardous Substances Data)

Usage

Description

1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol, also known as Ambrein, is a triterpenoid alcohol that is a constituent of ambergris, an intestinal secretion of the sperm whale Physeter catodon. It is the likely precursor of a number of strongly odoriferous mono-, bi-, and tricyclic compounds that are formed by autoxidation or photooxidation.

Uses

Used in Fragrance Industry:
1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol is used as a fixative and base note ingredient for its strong and long-lasting odoriferous properties, providing a pleasant and unique scent to perfumes and fragrances.
Used in Cosmetics Industry:
In the cosmetics industry, 1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol is used as an ingredient to enhance the fragrance and improve the longevity of scent in various cosmetic products such as lotions, creams, and soaps.
Used in Pharmaceutical Industry:
1-(6-(2,2-dimethyl-6-methylenecyclohexyl)-4-methylhex-3-enyl)decahydro-2,5,5,8a-tetramethyl-2-naphthol may also find applications in the pharmaceutical industry due to its potential biological activities and chemical properties, which could be harnessed for the development of new drugs or drug delivery systems.

InChI:InChI=1/C30H52O/c1-22(15-16-24-23(2)13-10-18-27(24,3)4)12-9-14-26-29(7)20-11-19-28(5,6)25(29)17-21-30(26,8)31/h12,24-26,31H,2,9-11,13-21H2,1,3-8H3/b22-12+/t24-,25?,26?,29+,30-/m1/s1

Synthetic route

(1R,2R,4aS,8aS,3'E,1"S)-(+)-1-[6'-(2",2"-dimethyl-6"-methylenecyclohexyl)-4'-methyl-3-hexenyl]-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-tetrahydropyranyloxy-2,5,5,8a-tetramethylnaphthalene → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) + (1R,2R,4aS,8aS)-1-[(Z)-6-((S)-2,2-Dimethyl-6-methylene-cyclohexyl)-4-methyl-hex-3-enyl]-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-ol

Conditions	Yield
With bis(trimethylsilyl)sulphate In 1,2-dichloro-ethane for 0.0333333h; Ambient temperature;	A 79% B n/a

<1R<2'RS,3'E(1'')R>,2R,4aS,8aS>-(+)-1-<2'-acetoxy-6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methyl-3'-hexenyl>-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-2,5,5,8a-tetramethylnaphthalene (124462-97-1, 124579-43-7) → (1R,2R,4aS,8aS)-1-[(E)-6-((S)-2,2-Dimethyl-6-methylene-cyclohexyl)-4-methyl-hex-2-enyl]-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-ol (124462-99-3) + (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
With hydrogenchloride; lithium; acetic acid; tert-butyl alcohol 1. ethylamine, -78 deg C, 10 min 2. room temperature; Yield given. Multistep reaction. Yields of byproduct given;

(4aR,6aS,10aS,10bR)-(-)-2,3,4a,5,6,6a,7,8,9,10,10a,10b-dodecahydro-4a,7,7,10a-tetramethyl-naphtho<2,1-b>pyran-3-ol (13017-23-7) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 8 steps 1: 90.1 percent / benzene / 15 h / 70 °C 2: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 3: 96.2 percent / LiAlH4 4: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 5: dimethylformamide / 12 h / Ambient temperature 6: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 7: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 8: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 8 steps 1: 90.1 percent / benzene / 15 h / 70 °C 2: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 3: 96.2 percent / LiAlH4 4: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 5: dimethylformamide / 12 h / Ambient temperature 6: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 7: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 8: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(S)-(+)-(2',2'-dimethyl-6'-methylene-1'-cyclohexyl)methanol (166022-29-3) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: pyridine / 1 h / 0 °C 2: NaBr / dimethylformamide / 5 h / 90 °C 3: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 4: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 5: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 4 steps 1: 80 percent / CCl4, trioctylphosphine / 75 °C 2: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 3: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 4: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(1S)-(+)-2,2-dimethyl-6-methylene-1-cyclohexanecarboxylic acid (166022-22-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 7 steps 1: 99.4 percent 2: 90.6 percent / LiAlH4 3: pyridine / 1 h / 0 °C 4: NaBr / dimethylformamide / 5 h / 90 °C 5: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 6: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 7: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 6 steps 1: 99.4 percent 2: 90.6 percent / LiAlH4 3: 80 percent / CCl4, trioctylphosphine / 75 °C 4: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 5: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 6: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

methyl (1S)-(+)-2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (166239-08-3) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: 90.6 percent / LiAlH4 2: pyridine / 1 h / 0 °C 3: NaBr / dimethylformamide / 5 h / 90 °C 4: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 5: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 6: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 5 steps 1: 90.6 percent / LiAlH4 2: 80 percent / CCl4, trioctylphosphine / 75 °C 3: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 4: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 5: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

Methanesulfonic acid (1S,2R,4aS,8aS)-2,5,5,8a-tetramethyl-2-(tetrahydro-pyran-2-yloxy)-decahydro-naphthalen-1-ylmethyl ester (188539-96-0) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 11 steps 1: 1.) NaOMe, 2.) 18-crown-6 / 1) MeOH, 30 deg C, 30 min; 2) MeOH, HMPA, 68 deg C, 12 h 2: 92.1 percent / KOH / ethanol / 1.5 h / 55 °C 3: 71.1 percent / DIBAL / toluene / 1 h / -65 °C 4: 90.1 percent / benzene / 15 h / 70 °C 5: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 6: 96.2 percent / LiAlH4 7: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 8: dimethylformamide / 12 h / Ambient temperature 9: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 10: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 11: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 11 steps 1: 1.) NaOMe, 2.) 18-crown-6 / 1) MeOH, 30 deg C, 30 min; 2) MeOH, HMPA, 68 deg C, 12 h 2: 92.1 percent / KOH / ethanol / 1.5 h / 55 °C 3: 71.1 percent / DIBAL / toluene / 1 h / -65 °C 4: 90.1 percent / benzene / 15 h / 70 °C 5: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 6: 96.2 percent / LiAlH4 7: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 8: dimethylformamide / 12 h / Ambient temperature 9: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 10: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 11: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(S)-2-Chloromethyl-1,1-dimethyl-3-methylene-cyclohexane (188559-02-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 2: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 3: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(S)-2-Bromomethyl-1,1-dimethyl-3-methylene-cyclohexane (188559-03-7) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 2: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 3: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

Methanesulfonic acid (S)-2,2-dimethyl-6-methylene-cyclohexylmethyl ester (188540-03-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: NaBr / dimethylformamide / 5 h / 90 °C 2: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 3: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 4: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

2-[(1R,2R,4aS,8aS)-1-((E)-5-Chloro-4-methyl-pent-3-enyl)-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-yloxy]-tetrahydro-pyran (120931-38-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: dimethylformamide / 12 h / Ambient temperature 2: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 3: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 4: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 4 steps 1: dimethylformamide / 12 h / Ambient temperature 2: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 3: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 4: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(E)-2-Methyl-5-[(1R,2R,4aS,8aS)-2,5,5,8a-tetramethyl-2-(tetrahydro-pyran-2-yloxy)-decahydro-naphthalen-1-yl]-pent-2-en-1-ol (188540-00-3) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 2: dimethylformamide / 12 h / Ambient temperature 3: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 4: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 5: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 5 steps 1: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 2: dimethylformamide / 12 h / Ambient temperature 3: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 4: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 5: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(E)-2-Methyl-5-[(1R,2R,4aS,8aS)-2,5,5,8a-tetramethyl-2-(tetrahydro-pyran-2-yloxy)-decahydro-naphthalen-1-yl]-pent-2-enoic acid methyl ester (188539-99-3) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: 96.2 percent / LiAlH4 2: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 3: dimethylformamide / 12 h / Ambient temperature 4: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 5: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 6: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 6 steps 1: 96.2 percent / LiAlH4 2: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 3: dimethylformamide / 12 h / Ambient temperature 4: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 5: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 6: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

2-[(1R,2R,4aS,8aS)-2,5,5,8a-Tetramethyl-2-(tetrahydro-pyran-2-yloxy)-decahydro-naphthalen-1-ylmethyl]-malonic acid dimethyl ester (188539-97-1) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 10 steps 1: 92.1 percent / KOH / ethanol / 1.5 h / 55 °C 2: 71.1 percent / DIBAL / toluene / 1 h / -65 °C 3: 90.1 percent / benzene / 15 h / 70 °C 4: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 5: 96.2 percent / LiAlH4 6: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 7: dimethylformamide / 12 h / Ambient temperature 8: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 9: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 10: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 10 steps 1: 92.1 percent / KOH / ethanol / 1.5 h / 55 °C 2: 71.1 percent / DIBAL / toluene / 1 h / -65 °C 3: 90.1 percent / benzene / 15 h / 70 °C 4: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 5: 96.2 percent / LiAlH4 6: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 7: dimethylformamide / 12 h / Ambient temperature 8: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 9: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 10: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

2-{(1R,2R,4aS,8aS)-2,5,5,8a-Tetramethyl-1-[(E)-4-methyl-5-(toluene-4-sulfonyl)-pent-3-enyl]-decahydro-naphthalen-2-yloxy}-tetrahydro-pyran (188539-95-9) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 2: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 3: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 3 steps 1: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 2: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 3: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

2-{(1R,2R,4aS,8aS)-1-[(E)-6-((S)-2,2-Dimethyl-6-methylene-cyclohexyl)-4-methyl-5-(toluene-4-sulfonyl)-hex-3-enyl]-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-yloxy}-tetrahydro-pyran → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 2: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(E)-5-((1R,2R,4aS,8aS)-2-Hydroxy-2,5,5,8a-tetramethyl-decahydro-naphthalen-1-yl)-2-methyl-pent-2-enoic acid methyl ester (188539-98-2) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 7 steps 1: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 2: 96.2 percent / LiAlH4 3: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 4: dimethylformamide / 12 h / Ambient temperature 5: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 6: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 7: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 7 steps 1: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 2: 96.2 percent / LiAlH4 3: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 4: dimethylformamide / 12 h / Ambient temperature 5: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 6: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 7: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

ambreinolide (468-84-8) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 9 steps 1: 71.1 percent / DIBAL / toluene / 1 h / -65 °C 2: 90.1 percent / benzene / 15 h / 70 °C 3: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 4: 96.2 percent / LiAlH4 5: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 6: dimethylformamide / 12 h / Ambient temperature 7: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 8: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 9: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme
Multi-step reaction with 9 steps 1: 71.1 percent / DIBAL / toluene / 1 h / -65 °C 2: 90.1 percent / benzene / 15 h / 70 °C 3: 92.7 percent / TsOH / CH2Cl2 / 1 h / 0 °C 4: 96.2 percent / LiAlH4 5: 1.) LiCl, NaHCO3, 2,6-lutidine, 2.) MsCl / 1) DMF, 0 deg C, 50 min; 2) DMF, 0 deg C, 2.5 h 6: dimethylformamide / 12 h / Ambient temperature 7: 1.) BuLi / 1) hexane, THF, HMPA, -30 deg C, 15 min; 2) THF, hexane, HMPA, -30 --> 10 deg C, 3 h 8: PdCl2(dppp), LiHBEt3 / tetrahydrofuran / 8 h / 0 °C 9: 79 percent / bis(trimethylsilyl) sulfate / 1,2-dichloro-ethane / 0.03 h / Ambient temperature View Scheme

(1R,2R,4aS,8aS)-1-(2-hydroxyethyl)-2,5,5,8a-tetramethyl-decahydronaphthalen-2-ol (38419-75-9) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 99 percent / pyridine / CH2Cl2 / 12 h / Ambient temperature 2: 84 percent / diisopropylethylamine / 1,2-dichloro-ethane / 12 h / Ambient temperature 3: 98 percent / K2CO3 / methanol / 12 h / Ambient temperature 4: 96 percent / pyridinium dichromate / CH2Cl2 / 2 h / Ambient temperature 6: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 7: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

ethyl (1R,3S)-3-hydroxy-2,2-dimethyl-6-methylenecyclohexaneacetate (124177-09-9) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions

Yield

Multi-step reaction with 8 steps 1: 100 percent / LiAlH4 / CH2Cl2 / 20 h / Ambient temperature 2: 98 percent / NEt3 / CH2Cl2 / 20 h / Ambient temperature 3: 1. n-butyllithium, N,N,N',N'-tetramethylethylendiamine / 1. n-hexane, 1,2-dimethoxyethane, 2 h, room temperature 2. 20 h, room temperature 5: 78 percent / K2CO3 / methanol / 12 h / Ambient temperature 7: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 8: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1S)-(-)-1-(3'-butynyl)-2,2-dimethyl-6-methylenecyclohexane (124462-79-9) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 3 steps 2: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 3: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1R,3S)-2-(-)-3-hydroxy-2,2-dimethyl-6-methylene-1-cyclohexaneethanol (124462-82-4) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 98 percent / NEt3 / CH2Cl2 / 20 h / Ambient temperature 2: 1. n-butyllithium, N,N,N',N'-tetramethylethylendiamine / 1. n-hexane, 1,2-dimethoxyethane, 2 h, room temperature 2. 20 h, room temperature 4: 78 percent / K2CO3 / methanol / 12 h / Ambient temperature 6: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 7: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1S)-(-)-2,2-dimethyl-6-methylene-1-<4'-(trimethylsilyl)-3'-butynyl>cyclohexane (124462-90-4) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 78 percent / K2CO3 / methanol / 12 h / Ambient temperature 3: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 4: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1R,2R,4aS,8aS)-(-)-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-2,5,5,8a-tetramethylnaphthaleneethanol (124462-94-8) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 96 percent / pyridinium dichromate / CH2Cl2 / 2 h / Ambient temperature 3: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 4: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1S,2R)-(-)-3-<2'-(tert-butyldimethylsilyloxy)ethyl>-2,2-dimethyl-4-methylene-1-cyclohexanol (124462-83-5) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions

Yield

Multi-step reaction with 6 steps 1: 1. n-butyllithium, N,N,N',N'-tetramethylethylendiamine / 1. n-hexane, 1,2-dimethoxyethane, 2 h, room temperature 2. 20 h, room temperature 3: 78 percent / K2CO3 / methanol / 12 h / Ambient temperature 5: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 6: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1R,2R,4aS,8aS)-(-)-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-2,5,5,8a-tetramethylnaphthaleneacetaldehyde (124462-93-7) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 3 steps 2: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 3: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1R,2R,4aS,8aS)-(-)-1-(2'-acetoxyethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-2,5,5,8a-tetramethylnaphthalene (124462-92-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: 98 percent / K2CO3 / methanol / 12 h / Ambient temperature 2: 96 percent / pyridinium dichromate / CH2Cl2 / 2 h / Ambient temperature 4: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 5: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

C21H45N2O3PSi (124462-84-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 5 steps 2: 78 percent / K2CO3 / methanol / 12 h / Ambient temperature 4: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 5: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

<1R<2'RS,3'E(1'')R>,2R,4aS,8aS>-(-)-1-<6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-2'-hydroxy-4'-methyl-3'-hexenyl>-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-2,5,5,8a-tetramethylnaphthalene (124462-96-0, 124579-42-6) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 2: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1R,2R,4aS,8aS)-(+)-1-(2'-acetoxyethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-hydroxy-2,5,5,8a-tetramethylnaphthalene (64061-39-8) → (1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0)

Conditions

Yield

Multi-step reaction with 6 steps 1: 84 percent / diisopropylethylamine / 1,2-dichloro-ethane / 12 h / Ambient temperature 2: 98 percent / K2CO3 / methanol / 12 h / Ambient temperature 3: 96 percent / pyridinium dichromate / CH2Cl2 / 2 h / Ambient temperature 5: 81 percent / pyridine, 4-(dimethylamino)pyridine / 12 h / Ambient temperature 6: 1. Li, t-BuOH 2. dil. HCl, 80percent aq. AcOH / 1. ethylamine, -78 deg C, 10 min 2. room temperature View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → (1R,2R,4aS,8aS,3'S,4'S,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-hydroxy-4'-methylhexyl]-2,3'-epoxy-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol + (+)-(S)-dihydro-γ-ionone (24190-33-8)

Conditions	Yield
In water; acetone at 20℃; for 72h; UV-irradiation;	A 8.3% B 6 mg

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → (1R,2R,4aS,8aS,3'E,5'S,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methyl-5'-hydroxyhex-3'-enyl]-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol + (1R,2R,4aS,8aS,3'E,5'R,1''S)-(-)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methyl-5'-hydroxyhex-3'-enyl]-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol + (1R,2R,4aS,8aS,3'E,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-hydroxymethylhex-3'-enyl]-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol + (1R,2R,4aS,8aS,3'E,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methyl-5'-oxohex-3'-enyl]-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol

Conditions	Yield
With selenium(IV) oxide In 1,4-dioxane at 20℃; for 1h;	A 7.5% B 7.6% C 4.9% D 0.75%

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → (1R,2R,4aS,8aS,3'R,4'E,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methylhex-4'-enyl]-2,3'-epoxy-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol

Conditions	Yield
Multi-step reaction with 2 steps 1: 7.6 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: 20.8 percent / p-toluenesulfonyl chloride; pyridine / 12 h / 50 °C View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → (1R,2R,4aS,8aS,5'S,3'E,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methylhex-3'-enyl]-2,5'-epoxy-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol

Conditions	Yield
Multi-step reaction with 2 steps 1: 7.6 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: 43.8 percent / p-toluenesulfonyl chloride; pyridine / 12 h / 50 °C View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → C40H59O4F3

Conditions	Yield
Multi-step reaction with 2 steps 1: 7.5 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: pyridine / 7 h / 20 °C View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → C40H59O4F3

Conditions	Yield
Multi-step reaction with 2 steps 1: 7.5 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: pyridine / 7 h / 20 °C View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → C40H59O4F3

Conditions	Yield
Multi-step reaction with 2 steps 1: 7.6 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: pyridine / 7 h / 20 °C View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → C40H59O4F3

Conditions	Yield
Multi-step reaction with 2 steps 1: 7.6 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: pyridine / 7 h / 20 °C View Scheme

(1R,4aα)-1-[(E)-6-[(S)-2,2-dimethyl-6-methylenecyclohexyl]-4-methyl-3-hexenyl]decahydro-2,5,5,8aβ-tetramethylnaphthalene-2α-ol (473-03-0) → (1R,2R,4aS,8aS,3'E,1''S)-(+)-1-[6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-benzoyloxymethylhex-3'-enyl]-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol

Conditions	Yield
Multi-step reaction with 2 steps 1: 4.9 percent / selenium dioxide / dioxane / 1 h / 20 °C 2: 12.2 percent / pyridine / 15 h / 50 °C View Scheme

Upstream product

• 10281-49-9 2-{(1S,2R,4aR,8aS)-1-[(E)-6-(2,2-Dimethyl-6-methylene-cyclohexyl)-4-methyl-hex-3-enyl]-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-yloxy}-tetrahydro-pyran 
• 432-23-5 2,2-dimethyl-6-methylenecyclohexane-1-carbaldehyde 
• 35071-26-2 1-bromomethyl-3,3-dimethyl-1-cyclohexene 
• 472-19-5 (2,2-dimethyl-6-methylenecyclohexyl)methanol 
• 120931-39-7 (+/-)-γ-cyclogeranyl chloride 
• 13017-23-7 (4aR,6aR,10aS,10bS)-4a,7,7,10a-Tetramethyl-dodecahydro-benzo[f]chromen-3-ol 
• 120931-35-3 Acetic acid (E)-5-((1S,2R,4aR,8aS)-2-hydroxy-2,5,5,8a-tetramethyl-decahydro-naphthalen-1-yl)-2-methyl-pent-2-enyl ester 
• 120931-37-5 Acetic acid (E)-2-methyl-5-[(1S,2R,4aR,8aS)-2,5,5,8a-tetramethyl-2-(tetrahydro-pyran-2-yloxy)-decahydro-naphthalen-1-yl]-pent-2-enyl ester 
• 468-84-8 (+)-ambreinolide 
• 30154-33-7 (1S,2R,4aR,8aS)-1-((E)-5-Hydroxy-4-methyl-pent-3-enyl)-2,5,5,8a-tetramethyl-decahydro-naphthalen-2-ol 
• 30154-32-6 (E)-5-((1S,2R,4aR,8aS)-2-Hydroxy-2,5,5,8a-tetramethyl-decahydro-naphthalen-1-yl)-2-methyl-pent-2-enoic acid ethyl ester 
• 124462-97-1 <1R<2'RS,3'E(1'')R>,2R,4aS,8aS>-(+)-1-<2'-acetoxy-6'-(2'',2''-dimethyl-6''-methylenecyclohexyl)-4'-methyl-3'-hexenyl>-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-2,5,5,8a-tetramethylnaphthalene 
• 13017-23-7 (4aR,6aS,10aS,10bR)-(-)-2,3,4a,5,6,6a,7,8,9,10,10a,10b-dodecahydro-4a,7,7,10a-tetramethyl-naphtho<2,1-b>pyran-3-ol 
• 166022-29-3 (S)-(+)-(2',2'-dimethyl-6'-methylene-1'-cyclohexyl)methanol 

Downstream Products

• 468-84-8 ambreinolide 
• 564-20-5 (3aR)-(+)-sclareolide 
• 575-43-9 1,6-dimethylnaphthalene 
• 641-91-8 1,2,5-trimethylnaphthalene 
• 64-18-6 formic acid 
• 65716-58-7 (S)-1.1-dimethyl-2-(3-oxo-butyl)-cyclohexanone-⁽³⁾ 
• 24190-33-8 (+)-(S)-dihydro-γ-ionone 
• 111319-84-7 drimenic acid 
• 10410-86-3 8-hydroxy-14,15,16-trinor-labdan-13-al-(2,4-dinitro-phenylhydrazone) 

Relevant articles and documents

Cyclization of squalene from both termini: Identification of an onoceroid synthase and enzymatic synthesis of ambrein

The onoceroids are triterpenoids biosynthesized from squalene or (3S)-2,3-oxidosqualene by cyclization from both termini. We recently revealed that tetraprenyl-β-curcumene cyclase from Bacillus megaterium (BmeTC) is a bifunctional triterpene/sesquarterpene cyclase that converts head-to-tail tetraprenyl-β-curcumene and tail-to-tail squalene into pentacyclic and bicyclic products, respectively, in vivo. Here, we reveal that BmeTC has an unprecedented catalytic function in cyclizing squalene from both termini and is the first onoceroid synthase. We also report the first onoceroids from bacterial origin. Our discoveries suggest that symmetric and asymmetric onoceroids could be biosynthesized by a single enzyme via an intermediate cyclized at one terminus of squalene. Furthermore, the new function of BmeTC enabled the synthesis of (+)-ambrein, a major constituent of ambergris that is difficult to obtain naturally, via a mutated squalene-hopene cyclase-catalyzed reaction from easily available squalene.

METHOD FOR PRODUCING AMBREIN

Provided is a method for producing ambrein, comprising reacting tetraprenyl-β-curcumene cyclase with 3-deoxyachilleol A to obtain ambrein.

Triterpenoid Total Synthesis, I: Synthesis of Ambrein and Ambrox

The first total synthesis of (+)-ambrein (1), a triterpene alcohol isolated from ambergris, was achieved.Both the enantiomers of ambrox (2) were also synthesized.