Asymmetric hydrovinylation reaction.

Carbon-carbon bond-forming reactions are among the most important types of bond constructions in organic chemistry. Yet, the paucity of methods for the stereoselective incorporation of abundantly available carbon feedstocks such as CO, CO2, HCN, or simple olefins to prochiral substrates is one of the major limitations in this area.1 Ideally, from a manufacturing perspective, these reactions should proceed near ambient conditions under the influence of a catalyst capable of delivering very high turnover frequencies (number of moles of product/mole of catalyst/unit time) and high regioand stereoselectivities. In addition to the obvious economic benefits, such reactions would also enrich our repertoire of environmentally benign chemical processes. One potentially important class of such reactions is the [Ni+-H]-catalyzed oligomerization of olefins, which forms the basis of the dimersol technology (olefin dimerization, eq 1)2 and the shell higher olefin process (SHOP, eq 2).3 These two immensely successful commercial processes showcase the rewards of modern organometallic research, especially of the role of catalyst tuning to achieve highly selective carbon-carbon bond-forming reactions. The catalytic dimerization of propene proceeds with an astonishingly high rate of over 625 000 [propene][Ni]-1 [h]-1) for the precatalyst, [η-(allyl)Ni(PR3)] [RAlX3], making this one of the best homogeneously catalyzed reactions known.4 Applications of this chemistry for the synthesis of fine chemicals have been the subject of much research ever since its initial discovery. Dr. RajanBabu had his early education in India at Kerala University and the Indian Institute of Technology, Madras. He obtained a Ph.D. degree from the Ohio State University in 1978 working with Professor Harold Shechter, and was a postdoctoral fellow at Harvard University with the late Professor R. B. Woodward. He then joined the research staff of DuPont Central Research and Development, becoming a Research Fellow in 1993. He returned to Ohio State as a Professor of Chemistry in 1995. His primary research interests are in applications of organometallic reagents for stereoselective synthesis, asymmetric catalysis, free radical chemistry, and organic chemistry in aqueous medium. 2845 Chem. Rev. 2003, 103, 2845−2860