Catalytic Enantioselective Protoboration of Disubstituted Allenes. Access to Alkenylboron Compounds in High Enantiomeric Purity

摘要

Proto-boryl additions to 1,1-disubstituted allenes in the presence of 1.0?5.0 mol % of chiral NHC?Cu complexes, B_2(pin)_2, and t-BuOH proceed to afford alkenyl?B(pin) products in up to 98% yield, >98:2 site selectivity, and 98:2 er. The enantiomerically enriched alkenylboron products can be converted to otherwise difficult-to-access alkenyl bromides, methyl ketones or carboxylic acids. What’s more, the corresponding boronic acids may be used in highly stereoselective NHC?Cu-catalyzed allylic substitution reactions.