A Highly Efficient Gold‐Catalyzed Photoredox α‐C(sp3)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 [Au 2 (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.