Tunable Phosphoramidite Ligands for Asymmetric Hydrovinylation: Ligands par excellence for Generation of All-Carbon Quaternary Centers

α-Alkylstyrenes undergo efficient hydrovinylation (addition of ethene) in the presence of a nickel catalyst prepared from [(ally])NiBr] 2 , Na + [BAr 4 ] ― [Ar = 3,5-bis(trifluoromethyl)phenyl], and a phosphoramidite ligand giving products in excellent yields and enantioselectivities. In many cases phosphoramidites derived from achiral 2,2'-biphenol are almost as good as ligands derived from the more expensive enantiopure 1,1'-bi(2-naphthol)s. The hydrovinylation products, which carry two versatile latent functionalities, an aryl and a vinyl group, are potentially useful for the synthesis of several important natural products containing benzylic all-carbon quaternary centers.