Cyclopropanation of Alkenes via a Siloxycarbene–Palladium Complex

Key words

palladium catalysis - homoenolates - carbenes

Significance

The authors reveal that, under palladium catalysis, an acylsilane can serve as a source of an electron-rich carbene to undergo cyclopropanation with an alkene. The corresponding siloxy cyclopropanes serve as valuable homonenolates, as demonstrated through various derivatizations.

Comment

Both electron-neutral and electron-rich alkenes were compatible substrates in the ­cyclopropanation; however, electron-rich alkenes were more reactive, suggesting an electrophilic metal carbene species is involved in the catalytic pathway. DFT studies indicate that the mechanism of the cyclopropanation proceeds through a [2+2] cycloaddition to form a palladocyclobutane intermediate.

Publication History

Article published online:
18 March 2022