title: Chemoselective Silylative Reduction of Conjugated Nitriles under Metal-Free Catalytic Conditions: β-Silyl Amines and Enamines.
abstract: The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β-silyl amine, thus forming a new C(sp(3))-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes.
authors.affiliation: Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701 (Korea).|Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea).
authors.forename: Narasimhulu
authors.initials: N
authors.lastname: Gandhamsetty
authors.affiliation: Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701 (Korea).|Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea).
authors.forename: Juhyeon
authors.initials: J
authors.lastname: Park
authors.affiliation: Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701 (Korea).|Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea).
authors.forename: Jinseong
authors.initials: J
authors.lastname: Jeong
authors.affiliation: Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701 (Korea).|Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea).
authors.forename: Sung-Woo
authors.initials: SW
authors.lastname: Park
authors.affiliation: Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701 (Korea).|Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea).
authors.forename: Sehoon
authors.initials: S
authors.lastname: Park
authors.affiliation: Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701 (Korea). sbchang@kaist.ac.kr.|Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea). sbchang@kaist.ac.kr.
authors.forename: Sukbok
authors.initials: S
authors.lastname: Chang
keywords: boron; conjugation; hydrosilylation; reduction; synthetic methods