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

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.