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Chiral Acylsilanes in Organic Synthesis. Part 3. Silicon-directed stereoselective preparation and Ireland ester-enolate rearrangement of O-acyl-substituted α-silylated allyl alcohols


Enev, Valentin; Stojanova, Diana; Bienz, Stefan (1996). Chiral Acylsilanes in Organic Synthesis. Part 3. Silicon-directed stereoselective preparation and Ireland ester-enolate rearrangement of O-acyl-substituted α-silylated allyl alcohols. Helvetica Chimica Acta, 79(2):391-404.

Abstract

Stereocontrolled addition of alk-1-enylmetal reagents to the chiral (alkoxymethyl)-substituted acylsilanes (±)-6 gave rise to α-silylated allyl alcohols, which were converted to the corresponding acetates or propionates 11–16 (Scheme 2). Deprotonation and silylation with Me3SiCl afforded – in an Ireland ester-enolate-accelerated Claisen rearrangement – stereoselectively αδ-silylated γδ-unsaturated carboxylic acids 18–24 (Scheme 4). The Me3Si groups in α-position to the COOH group of these compounds were removed chemoselectively in presence of the chiral silyl group in δ-position by treatment with Bu4NF · 3 H2O or Et3N · 3 HF (→ 27–32; Scheme 5). The reaction sequence allows a novel stereocontrolled access to chiral C-frameworks possessing a vinylsilane moiety with its full reaction potential.

Abstract

Stereocontrolled addition of alk-1-enylmetal reagents to the chiral (alkoxymethyl)-substituted acylsilanes (±)-6 gave rise to α-silylated allyl alcohols, which were converted to the corresponding acetates or propionates 11–16 (Scheme 2). Deprotonation and silylation with Me3SiCl afforded – in an Ireland ester-enolate-accelerated Claisen rearrangement – stereoselectively αδ-silylated γδ-unsaturated carboxylic acids 18–24 (Scheme 4). The Me3Si groups in α-position to the COOH group of these compounds were removed chemoselectively in presence of the chiral silyl group in δ-position by treatment with Bu4NF · 3 H2O or Et3N · 3 HF (→ 27–32; Scheme 5). The reaction sequence allows a novel stereocontrolled access to chiral C-frameworks possessing a vinylsilane moiety with its full reaction potential.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:20 March 1996
Deposited On:24 Aug 2017 16:19
Last Modified:20 Feb 2018 08:51
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:0018-019X
OA Status:Closed
Publisher DOI:https://doi.org/10.1002/hlca.19960790208

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