Stereoselective Cyclopropanation of 1,1-Diborylalkenes via Palladium-Catalyzed (Trimethylsilyl)diazomethane Insertion

Identifier:  imarina:9280225

Handle: https://hdl.handle.net/20.500.11797/imarina9280225

Authors:  Salvado, O; Dominguez-Molano, P; Fernandez, E

Abstract:
Palladium catalyzes the cydclopropanation of 2-substituted 1,1-diborylalkenes with (trimethylsilyl)diazomethane. The relative stereoselectivity is controlled via a carbene insertion sequence generating an exclusive anti conformation between the R and SiMe3 substituents. Mixed 1,1-diborylalkenes also contributed to the formation of stereoselective B, B, Si-cyclopropanes. Orthogonal activation with (NaOBu)-Bu-t gives protodeborylation preferentially on the boron moiety syn to the aryl group. Further oxidation gives access to polyfunctional cycloopropyl alcohols with controlled enantioselectivity when chiral boryl motifs are involved.