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Synthesis of silyloxy dienes by silylene transfer to divinyl ketones: application to the asymmetric synthesis of substituted cyclohexanes.

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.

SUBMITTER: Ventocilla CC

PROVIDER: S-EPMC3336154 | biostudies-literature | 2012 Apr

REPOSITORIES: biostudies-literature

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Synthesis of silyloxy dienes by silylene transfer to divinyl ketones: application to the asymmetric synthesis of substituted cyclohexanes.

Ventocilla Christian C CC Woerpel K A KA

The Journal of organic chemistry 20120316 7

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 ...[more]

PMID: 22372733

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