title: Catalytic Coupling between Unactivated Aliphatic C-H Bonds and Alkynes via a Metal-Hydride Pathway.
abstract: We report a Rh(I)-catalyzed site-selective coupling between ketone β-C(sp3)-H bonds and aliphatic alkynes using an in situ-installed directing group. Upon hydrogenation or hydration, various β-alkylation or β-aldol products of the ketones are obtained with broad functional group tolerance. Mechanistic investigations support the involvement of a Rh-H intermediate through oxidative addition of Rh(I) into the β-C-H bonds. Thus, to the best of our knowledge, this transformation represents the first example of catalytic couplings between unsaturated hydrocarbons and unactivated aliphatic C-H bonds via a metal-hydride pathway.
authors.affiliation: Department of Chemistry, University of Chicago , Chicago, Illinois 60637, United States.|Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Yan
authors.initials: Y
authors.lastname: Xu
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Michael C
authors.initials: MC
authors.lastname: Young
authors.affiliation: Department of Chemistry, University of Chicago , Chicago, Illinois 60637, United States.|Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Guangbin
authors.identifier: 0000-0003-1331-6015
authors.initials: G
authors.lastname: Dong