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Pure Appl. Chem., 2004, Vol. 76, No. 3, pp. 465-475

Rhodium-catalyzed asymmetric addition of aryl- and alkenylboron reagents to electron-deficient olefins

T. Hayashi

Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan

Abstract: Asymmetric 1,4-arylation and -alkenylation was achieved by use of organoboronic acids or their derivatives in the presence of a rhodium catalyst coordinated with binap or its related ligands. The scope of this asymmetric addition is very broad, α, β-unsaturated ketones, esters, amides, 1-alkenylphosphonates, and 1-nitroalkenes being efficiently converted into the corresponding 1,4-addition products with over 95% enantioselectivity. The catalytic cycle in water is proposed to involve three intermediates [aryl-or alkenyl-rhodium (oxa-π-allyl) rhodium, and hydroxo-rhodium] by NMR studies on the rhodium intermediates.