New catalytic reactions of oxa- and azabicyclic alkenes

Abstract

Bicyclic alkenes, including oxa- and azabenzonorbornadienes and their derivatives, can be readily activated by transition metal complexes face-selectively due to their unsymmetrical bicyclic structure and the intrinsic angle strain on the carbon-carbon double bond. We have developed several stereo-, regio-, and chemoselective reactions catalyzed by nickel and palladium complexes using these bicyclic alkenes as substrates, providing a unique means of constructing a variety of synthetically useful carbocycles and heterocycles with high efficiency not generally accessible by traditional methods. This Account outlines these new metal-catalyzed reactions that include couplings, cycloadditions, and cyclization reactions.