title: Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.
abstract: A copper-catalyzed, chemoselective hydrometalation process enables the use of simple allenes as allylmetal nucleophile surrogates in imine allylation reactions. By modulating the nitrogen-protecting group, either highly branched- or linear-selective addition can be achieved from the same allene. Both reactions exhibit excellent diastereoselectivity and broad functional-group tolerance. Preliminary results indicate that good enantioselectivity can also be achieved in the linear-selective reaction. Finally, a mechanistic model for the regiodivergence is proposed on the basis of density functional theory calculations.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.
authors.forename: Richard Y
authors.initials: RY
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.
authors.forename: Yang
authors.initials: Y
authors.lastname: Yang
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA. sbuchwal@mit.edu.
authors.forename: Stephen L
authors.initials: SL
authors.lastname: Buchwald
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D000478:Alkylation; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D000588:Amines; D007097:Imines; D003300:Copper
keywords: C−C coupling; amines; copper; multicomponent reactions; regioselectivity