Palladium-Catalyzed Siloxycyclopropanation of Alkenes Using Acylsilanes

Currently, catalytically transferable carbenes are limited to electron-deficient and neutral derivatives, and electron-rich carbenes bearing an alkoxy group (i.e., Fischer-type carbenes) cannot be used in catalytic cyclopropanation because of the lack of appropriate carbene precursors. We report herein that acylsilanes can serve as a source of electron-rich carbenes under palladium catalysis, enabling cyclopropanation of a range of alkenes. This reactivity profile is in sharp contrast to that of metal-free siloxycarbenes, which are unreactive toward normal alkenes. The resulting siloxycyclopropanes serve as valuable homoenolate equivalents, allowing rapid access to elaborate beta-functionalized ketones.

Automated summary

This study demonstrates that acylsilanes can serve as a source of electron-rich carbenes under palladium catalysis, enabling the cyclopropanation of alkenes. This new reactivity profile provides a valuable method for accessing elaborate beta-functionalized ketones.