title: Regiodivergent and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes.
abstract: Methods for the highly stereoselective and regiodivergent hydrosilylation of 1,3-disubstituted allenes have been developed. The synthesis of E allylsilanes is accomplished with palladium NHC catalysts, and trisubstituted Z alkenylsilanes are accessed with nickel NHC catalysts. Unsymmetrically substituted allenes are well tolerated with nickel catalysis and afford Z alkenylsilanes. Evidence for a plausible mechanism was obtained through an isotopic double-labeling crossover study.
authors.affiliation: Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109-1055 (USA) http://www.umich.edu/∼jmgroup.
authors.forename: Zachary D
authors.initials: ZD
authors.lastname: Miller
authors.affiliation: Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109-1055 (USA) http://www.umich.edu/∼jmgroup.
authors.forename: Ruth
authors.initials: R
authors.lastname: Dorel
authors.affiliation: Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109-1055 (USA) http://www.umich.edu/∼jmgroup. jmontg@umich.edu.
authors.forename: John
authors.initials: J
authors.lastname: Montgomery
keywords: hydrosilylation; regioselectivity; silanes; stereoselectivity; transition-metal catalysis