Regiodivergent and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes

Zachary D Miller; Ruth Dorel; John Montgomery

doi:10.1002/anie.201503521

Regiodivergent and Stereoselective Hydrosilylation of 1,3-Disubstituted Allenes

Angew Chem Int Ed Engl. 2015 Jul 27;54(31):9088-91. doi: 10.1002/anie.201503521. Epub 2015 Jun 16.

Authors

Zachary D Miller¹, Ruth Dorel¹, John Montgomery²

Affiliations

¹ Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109-1055 (USA) http://www.umich.edu/∼jmgroup.
² Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109-1055 (USA) http://www.umich.edu/∼jmgroup. jmontg@umich.edu.

PMID: 26079290
DOI: 10.1002/anie.201503521

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.

Keywords: hydrosilylation; regioselectivity; silanes; stereoselectivity; transition-metal catalysis.