title: A Highly Efficient Gold-Catalyzed Photoredox α-C(sp(3))-H Alkynylation of Tertiary Aliphatic Amines with Sunlight.
abstract: A new α-C(sp(3))H alkynylation of unactivated tertiary aliphatic amines with 1-iodoalkynes as radical alkynylating reagents in the presence of [Au2(μ-dppm)2](2+) in sunlight provides propargylic amines. Based on mechanistic studies, a C-C coupling of an α-aminoalkyl radical and an alkynyl radical is proposed for the C(sp(3))-C(sp) bond formation. The mild, convenient, efficient, and highly selective C(sp(3))-H alkynylation reaction shows excellent regioselectivity and good functional-group compatibility. A scale-up to gram quantities is possible with sunlight used as a clean and sustainable energy source.
authors.affiliation: Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany) http://www.hashmi.de.
authors.forename: Jin
authors.initials: J
authors.lastname: Xie
authors.forename: Shuai
authors.initials: S
authors.lastname: Shi
authors.forename: Tuo
authors.initials: T
authors.lastname: Zhang
authors.forename: Nina
authors.initials: N
authors.lastname: Mehrkens
authors.forename: Matthias
authors.initials: M
authors.lastname: Rudolph
authors.forename: A Stephen K
authors.initials: AS
authors.lastname: Hashmi
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D006847:Hydrocarbons, Iodinated / Q000737:chemistry; D015394:Molecular Structure; D050607:Organogold Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D013237:Stereoisomerism; D013472:Sunlight
chemical_list: D000480:Alkynes; D000588:Amines; D006847:Hydrocarbons, Iodinated; D050607:Organogold Compounds
keywords: CH activation; gold catalysis; photoredox catalysis; radical CC coupling; sunlight