The Asymmetric Dihydroxylation of Some Alkenyl b-D-Glucopyranosides: the Preparation of an Optically Pure Episulfide

Peci, Lorenzo M.; Tilbrook, D. M. G.; Winslade, Merilyn

doi:10.1071/c97149

Cited by 5 publications

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Asymmetric Dihydroxylation of Alkenes

2005

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The oxidation of alkenes to vicinal diols using osmium tetroxide is one of the most selective and reliable transformations in organic synthesis. The reaction stereospecifically produces a cis‐1,2‐glycol and is tolerant of a wide array of functional groups. Methods have been developed to oxidize alkenes stoichiometrically, as well as in the presence of catalytic amounts of osmium tetroxide, when a suitable secondary oxidant is present. The latter process is particularly useful considering the expense and toxicity of osmium tetroxide. The utility of dihydroxylation in organic synthesis is enhanced by the facile transformations of the cis‐1,2‐diol products into other useful derivatives. Among the most versatile intermediates are the corresponding cyclic sulfates, which serve as reactive epoxide equivalents that can be used singly or doubly displaced with amine‐, oxygen‐, sulfur‐, or carbon‐based nucleophiles. The reaction of osmium tetroxide with alkenes is accelerated by several orders of magnitude in the presence of coordinating amine ligands such as triethylamine, quinuclidine, or diazobicyclooctane. The logical extension to asymmetric osmylation of alkenes in the presence of chiral amine bases spurred the study of asymmetric dihydroxylation. The breakthrough of catalytic turnover in the cinchona alkaloid‐osmium tetroxide system revolutionized the field of asymmetric dihydroxylation. Specialized ligands have been developed to provide position selectivity in the dihydroxylation of polyenes, efficient kinetic resolution of racemic substrates, and high levels of enantioselectivity for each of six alkene classes.

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Asymmetric Dihydroxylation of Alkenes

2005

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Sharpless Dihydroxylation

2010

Comprehensive Organic Name Reactions and Reagents

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This reaction is a transformation of olefins into syn ‐diols via an asymmetric cis ‐dihydroxylation in the presence of a catalytic amount of potassium osmate dihydrate using K 3 Fe(CN) 6 or NMO as an oxidant and is generally referred to as the Sharpless asymmetric dihydroxylation or Sharpless dihydroxylation. Generally, two reaction systems have been developed for the asymmetric transformation of olefins into syn ‐diols. The study finds that the reaction is especially suitable for the transformation of electron‐rich and sterically less hindered olefins. The Sharpless dihydroxylaton requires an enantiomerically pure molecule to induce the chirality, and many natural chiral molecules (e.g., alkaloids) are suitable for this purpose. Besides the dihydroxylation of olefins, the Sharpless asymmetric dihydroxylation has also been successfully used for the introduction of an α‐hydroxyl group adjacent to the carbonyl functionality, by means of the dihydroxylation of an enol ether. This reaction has a broad application in organic synthesis with respect to the preparation of molecules with syn ‐diol moieties.

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ChemInform Abstract: The Asymmetric Dihydroxylation of Some Alkenyl β‐D‐Glucopyranosides: The Preparation of an Optically Pure Episulfide.

Peci¹,

Tilbrook²,

Winslade³

1998

ChemInform

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TheAsymmetric Dihydroxylation of Some Alkenyl β-D-Glucopyranosides: The Preparation of an Optically Pure Episulfide.-With a view to obtaining a putative inhibitor (VI) of β-D-glucan hydrolases several alkenes such as (I) are treated under Sharpless conditions. It is noteworthy that under the conditions of the AD-mix-α the ratio of (II):(III) varies from 1:3 to 1:1 (some yields not given or in g). -(PECI, L. M.; STICK, R. V.; TILBROOK, D. M. G.; WINSLADE, M. L.; Aust.

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The Asymmetric Dihydroxylation of Some Alkenyl b-D-Glucopyranosides: the Preparation of an Optically Pure Episulfide

Cited by 5 publications

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Asymmetric Dihydroxylation of Alkenes

Asymmetric Dihydroxylation of Alkenes

Sharpless Dihydroxylation

ChemInform Abstract: The Asymmetric Dihydroxylation of Some Alkenyl β‐D‐Glucopyranosides: The Preparation of an Optically Pure Episulfide.

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