Preparation of a-substituted allylboronates by chemoselective iridium-catalyzed asymmetric allylic alkylation of 1-propenylboronates

Chiral alpha-substituted allylic boronates are attractive reagents that add to aldehydes with very high stereoselectivity. This study examined the feasibility of an improved method of preparation based on the catalytic asymmetric allylic alkylation of simple 3-hydroxy-1-propenylboronate derivatives with malonate anions. Whereas palladium catalysis failed in promoting the desired process, iridium catalysis led to a regioselective formation of the desired, branched allylboronates with up to 84% ee using a chiral monophosphoramidite ligand. This allylation reagent adds to aldehydes with high chirality transfer. A diastereoselective alkoxycyclization on the resulting homoallylic alcohols allows a separation of the epimeric E/Z isomers. (c) 2007 Elsevier Ltd. All rights reserved.