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Synthesis of Silyloxy Dienes by Silylene Transfer to Divinyl Ketones: Application to the Asymmetric Synthesis of Substituted Cyclohexanes

Author:
Ventocilla, Christian C., Woerpel, K. A.
Source:
Journal of organic chemistry 2012 v.77 no.7 pp. 3277-3283
ISSN:
1520-6904
Subject:
chemical structure, cycloaddition reactions, cyclohexanes, cyclohexenes, diastereoselectivity, imines, ketones, organic chemistry, oxidation, regioselectivity, stereochemistry
Abstract:
Silver-catalyzed silylene transfer to divinyl ketones provided 2-silyloxy-1,3-dienes with control of stereochemistry and regioselectivity. The products participated in Diels–Alder reactions with electron-deficient alkenes and imines to form six-membered-ring products diastereoselectively. Cycloaddition reactions with alkenes bearing chiral auxiliaries provided access to chiral, nonracemic cyclohexenes. The methodology, therefore, represents a synthesis of diastereomerically and enantiomerically pure products in a single flask. The highly substituted cyclohexene products could be functionalized stereoselectively to provide cyclohexanols after oxidation of the carbon–silicon bond.
Agid:
5499761