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Stereoselective preparation of 2-silylated 1,3-diols and the regioselectivity of their Peterson olefination


Fässler, Jürg; Linden, Anthony; Bienz, Stefan (1999). Stereoselective preparation of 2-silylated 1,3-diols and the regioselectivity of their Peterson olefination. Tetrahedron, 55(6):1717-1730.

Abstract

The reduction of the carbonyl group of ct-silylated aldols with complex hydrides was shown to proceed with high stereoselectivity. The center of chirality in the ¢t-position to the ketone, at the C-atom where the silicon group is attached, usually dominated the stereochemical control of the reaction. The presence of the ~-hydroxy functionality, however, also seems to be necessary for a high degree of selectivity. Peterson olefination of 2-silylated 1,3-diols afforded stereoselectively (E)-configured allylic alcohols as the major products. With KH as the base, the reaction proceeds predominantly in a syn-fashion, preferring to eliminate a syn- rather than an ant/-configured 13-hydroxysilane unit. Under 'silico-nucleophilic' conditions (OH- or F-), an anti-configured ~-hydroxysilane moiety can also be eliminated in an anti-fashion. This reaction is strongly preferred over the corresponding syn-elimination, but is still less prominent than a competitive syn-elimination of a syn-configured 13-hydroxysilane unit

Abstract

The reduction of the carbonyl group of ct-silylated aldols with complex hydrides was shown to proceed with high stereoselectivity. The center of chirality in the ¢t-position to the ketone, at the C-atom where the silicon group is attached, usually dominated the stereochemical control of the reaction. The presence of the ~-hydroxy functionality, however, also seems to be necessary for a high degree of selectivity. Peterson olefination of 2-silylated 1,3-diols afforded stereoselectively (E)-configured allylic alcohols as the major products. With KH as the base, the reaction proceeds predominantly in a syn-fashion, preferring to eliminate a syn- rather than an ant/-configured 13-hydroxysilane unit. Under 'silico-nucleophilic' conditions (OH- or F-), an anti-configured ~-hydroxysilane moiety can also be eliminated in an anti-fashion. This reaction is strongly preferred over the corresponding syn-elimination, but is still less prominent than a competitive syn-elimination of a syn-configured 13-hydroxysilane unit

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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
Uncontrolled Keywords:Aldols, Reduction, Regioselection, Stereoselection
Language:English
Date:1999
Deposited On:24 Aug 2017 15:03
Last Modified:20 Feb 2018 07:51
Publisher:Elsevier
ISSN:0040-4020
OA Status:Closed
Publisher DOI:https://doi.org/10.1016/S0040-4020(98)01194-6

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