1196-67-4Relevant articles and documents
Deep eutectic solvent-catalyzed Meyer-Schuster rearrangement of propargylic alcohols under mild and bench reaction conditions
Ríos-Lombardía, Nicolás,Cicco, Luciana,Yamamoto, Kota,Hernández-Fernández, José A.,Morís, Francisco,Capriati, Vito,García-álvarez, Joaquín,González-Sabín, Javier
, p. 15165 - 15168 (2020)
The Meyer-Schuster rearrangement of propargylic alcohols into α,β-unsaturated carbonyl compounds has been revisited by setting up an atom-economic process catalyzed by a deep eutectic solvent FeCl3·6H2O/glycerol. Isomerizations take place smoothly, at room temperature, under air and with short reaction times. The unique solubilizing properties of the eutectic mixture enabled the use of a substrate concentration up to 1.0 M with the medium being recycled up to ten runs without any loss of catalytic activity. This journal is
BICHROMATES DE PHOSPHONIUM: REACTIFS D'OXYDATION
Cristau, Henri-Jean,Torreilles, Eliane,Morand, Philippe,Christol, Henri
, p. 1775 - 1776 (1986)
The bisphosphonium bichromate 1, appears as particularly mild and selective for the oxidation of primary or secondary alcohols.It performs the oxidation of primary alcohols into aldehydes without further oxidation in acid and without double-bond isomerisation or migration for such alcohols as geraniol; it allows also the fully selective oxidation of benzylic or allylic alcohols versus aliphatic alcohols.
Synthetic approaches to mono- and bicyclic perortho-esters with a central 1,2,4-trioxane ring as the privileged lead structure in antimalarial and antitumor-active peroxides and clarification of the peroxide relevance
Griesbeck, Axel G.,Br?utigam, Maria,Kleczka, Margarethe,Raabe, Angela
, (2017)
The synthesis of 4-styryl-substituted 2,3,8-trioxabicyclo[3.3.1]nonanes, peroxides with the core structure of the bioactive 1,2,4-trioxane ring, was conducted by a multistep route starting from the aryl methyl ketones 1a-1c. Condensation and reduction/oxidation delivered enals 4a-4c that were coupled with ethyl acetate and reduced to the 1,3-diol substrates 6a-6c. Highly diastereoselective photooxygenation delivered the hydroperoxides 7a-7c and subsequent PPTS (pyridinium-p-toluenesulfonic acid)-catalyzed peroxyacetalization with alkyl triorthoacetates gave the cyclic peroxides 8a-8e. These compounds in general show only moderate antimalarial activities. In order to extend the repertoire of cyclic peroxide structure, we aimed for the synthesis of spiro-perorthocarbonates from orthoester condensation of β-hydroxy hydroperoxide 9 but could only realize the monocyclic perorthocarbonate 10. That the central peroxide moiety is the key structural motif in anticancer active GST (glutathione S-transferase)-inhibitors was elucidated by the synthesis of a 1,3-dioxane 15-with a similar substitution pattern as the pharmacologically active peroxide 11-via a singlet oxygen ene route from the homoallylic alcohol 12.
Stereodefined rhodium-catalysed 1,4-H/D delivery for modular syntheses and deuterium integration
Cheng, Bao,Fang, Huayi,Ma, Shengming,Qian, Hui,Wang, Weiyi,Yu, Yibo,Zhang, Xue
, p. 586 - 594 (2021/07/17)
Deuterium-incorporated compounds are of high interest owing to their importance in the pharmaceutical industry, organic synthesis and materials science. So far, the integration of deuterium into the inert, saturated magic methyl or methylene groups of covalent molecules remains challenging. Here, we present a 1,4-H delivery of allylic metallic species to provide a highly stereoselective and straightforward approach to 3-methyl-2(E)-enals or -enones from readily available 2,3-allenols and organoboronic acids. The reaction accommodates many synthetically versatile functional groups as well as multi-pharmacophores, and is not limited to the formation of 3-methyl derivatives. By applying 1,4-H or D delivery, deuterium atom(s) from differently deuterated allenols can be edited into the methyl or methylene groups of versatile organic skeletons, resulting in the efficient formation of 4-monodeuterated, 1,4- and 4,4-doubly deuterated, and 4,4,4-triply deuterated 2(E)-enals or -enones. These powerful platform molecules can provide straightforward paths to other deuterated compounds for different purposes. [Figure not available: see fulltext.].
Method for preparing olefine aldehyde through catalytic oxidation of enol ether
-
Paragraph 0082-0086; 0088, (2021/06/23)
The invention relates to the technical field of olefine aldehyde preparation, and provides a method for preparing olefine aldehyde through catalytic oxidation of enol ether. According to the invention, a palladium catalyst, a copper salt, a solvent and enol ether are mixed and subjected to a catalytic oxidation reaction to obtain olefine aldehyde. According to the method, the copper salt is used as the oxidizing agent, the mixed solvent of water and acetonitrile is used as the reaction solvent, and the volume ratio of water to acetonitrile in the mixed solvent is controlled to be (3-7): (3-7), so that the catalytic oxidation reaction can be smoothly carried out in the mixed solvent with a specific ratio, and the generation of palladium black precipitate can be avoided. The method provided by the invention has the advantages of simple steps, low reagent cost, no need of dangerous reagents, wide substrate adaptability and small catalyst dosage. Furthermore, octadecane mercaptan is added to promote the catalytic oxidation reaction, and when the dosage of the palladium catalyst is extremely low, the olefine aldehyde yield can be greatly increased by adding octadecane mercaptan.
Carbene-Catalyzed Formal [3+3] Cycloaddition Reaction for Access to Substituted 2-Phenylbenzothiazoles
Ni, Zhibin,Mou, Chengli,Zhu, Xun,Qi, Puying,Yang, Song,Chi, Yonggui Robin,Jin, Zhichao
supporting information, p. 492 - 495 (2020/01/24)
A carbene-catalyzed oxidative cycloaddition reaction is developed for efficient access to multi-functionalized 2-phenylbenzothiazoles. A broad scope of heavily substituted arenes bearing 2-benzothiazole groups have been prepared in good to excellent yields. The remote C(sp2)–H bond in the substituted arene products can be activated by Pd catalysts in regio-selective fashion with the direction of the 2-benzothiazole groups.