Copper-Catalyzed Regio-, Diastereo-, and Enantioselective Allylic Alkylation with 1,1-Diborylalkanes
Minjae Kim, G.N. Kim, Doyoon Kim, Seung Hwan Cho
Abstract
We report a copper-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of allyl bromides using 1,1-diborylalkanes as prochiral nucleophiles. This methodology employs copper(I) bromide as a catalyst, an ( R )-BINOL-derived phosphoramidite as a ligand, and lithium benzoate as a crucial additive. The reaction affords enantioenriched homoallylic boronic esters possessing vicinal stereocenters in good yields and high diastereo- and enantioselectivity. The developed method demonstrates a broad substrate scope with respect to a wide range of 1,1-diborylalkanes and allyl bromides. Mechanistic studies, including deuterium-labeling experiments and DFT calculations, provide insights into the reaction pathway and the origin of the stereoselectivity. The synthetic utility of this method is showcased through various transformations of the obtained enantioenriched homoallylic boronic esters into valuable chiral building blocks.