Synthesis and reactivity of chiral pentavalent bismuth derivatives

Abstract

Eight new pentavalent organobismuth derivatives were synthesized by the reactions of triphenylbismuth or phenyl-2,2"-biphenylenebismuth with chiral (1R)-(–)-camphor-10-sulfonic, (–)-menthyloxyacetic, or (R)-3-phenylbutyric acids. Enantioselective C-arylation of enolizable substrates with organobismuth reagents was carried out for the first time. Unlike iodine, sulfur, and selenium derivatives, which contain a five-membered heterocycle including the 2,2"-biphenylene fragment, phenyl-2,2"-biphenylene organobismuth analogs enter into C-arylation reactions accompanied by the selective transfer exclusively of the phenyl group to the organic substrate.