Enantioselective and Regioselective Nickel-Catalyzed Multicomponent Coupling of Chiral Allenes, Aromatic Aldehydes, and Silanes

Journal of the American Chemical Society 127(20), 7320-7321, DOI: 10.1021/ja0521831

A complex derived from Ni(cod)2 and NHC−IPr catalyzes a three-component coupling reaction involving allenes, aldehydes, and organosilanes and transfers the axial chirality of the allene to a stereogenic center in the product with very high fidelity. An unexpected regioselectivity is observed; favored are allylic rather than homoallylic alcohol derivatives, corresponding to the unusual process of coupling two electrophilic atoms: the allene sp and aldehyde carbon atoms. In all cases, high enantioselectivity, high Z/E selectivity, and, with differentially substituted allenes, high site selectivity are observed. This transformation represents the first enantioselective multicomponent coupling process of allenes.