A Novel Stereoselective Reaction Cascade Leading fromα-Silylated Allylic Alcohols to Aldol-Type Products

Fässler, Jürg; Enev, Valentin S.; Bienz, Stefan

doi:10.1002/(sici)1522-2675(19990407)82:4<561::aid-hlca561>3.0.co;2-u

Cited by 18 publications

(2 citation statements)

References 13 publications

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“…To obtain the desired 2,3‐ anti triol derivatives, stereoselective epoxydation of the resulting α‐silylated allyl alcohols 11 with several oxidants and the following hydrolysis reaction were carried out . The treatment of α‐silylated allyl alcohols 11 possessing various substituents and silyl groups with m ‐CPBA did not give the corresponding epoxides, but afforded the silyl‐migrated compounds 13 with excellent 2,3‐ anti selectivity in quantitative yields (Scheme ) . In addition, the desired epoxides as the precursor compounds of 2,3‐ anti triol derivatives were not obtained at all by using the epoxidation reaction of 11a with other oxidants, Sharpless–Katsuki asymmetric epoxidation reagents , Oxone® , hydrogen peroxide , sodium peroxide .…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of 1,2,3‐Triol Derivatives from α,β‐Unsaturated Acylsilanes

Honda

Nakamura

Sumigawa

et al. 2014

Heteroatom Chemistry

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The stereoselective synthesis of 1,2,3‐triol derivatives having contiguous stereogenic centers from α,β‐unsaturated acylsilanes 1 was described. The oxidation of an olefin moiety of 1 with osmium tetroxide proceeded smoothly to give the corresponding 2,3‐syn‐dihydroxyacylsilanes 2. The protection of two hydroxy groups of 2 followed by a nucleophilic reaction to the silyl carbonyl group gave the corresponding silylated triol derivatives (7 and 8) with high stereoselectivity, depending on the kind of nucleophilic reagents. The deprotection for 7 and 8 and the following protodesilylation gave two isomers of possible four 1,2,3‐triol derivatives. The stereoselective triol synthesis by asymmetric diolization of α‐silylated allyl alcohols 11 derived by nucleophilic addition to 1 was also investigated.

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Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of 1,2,3‐Triol Derivatives from α,β‐Unsaturated Acylsilanes

Honda

Nakamura

Sumigawa

et al. 2014

Heteroatom Chemistry

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“…Bienz et al reported a stereoselective tandem reaction which converted a-silylated allylic alcohols to aldol-type products by using epoxidizing reagents (Scheme 81). 98 They proposed that the reaction proceeded either by a cascade process involving epoxidation of the allylic-alcohol moiety followed by an acid-promoted semipinacol rearrangement, or through a rearrangement of the silanium ion intermediate to give the final products.…”

Section: Substrate Scope Of the Rearrangementmentioning

confidence: 99%