Combining Organocatalysis and Photoredox Catalysis: An Asymmetric Synthesis of Chiral β‐ Amino α‐ Substituted Tryptamines

A stereoselective synthesis of functionalized β‐ amino α‐ substituted tryptamines has been achieved by a sequential asymmetric organocatalytic three‐component electrophilic amination and photocatalyzed Friedel‐Crafts reaction of indoles with moderate to high diastereoselectivities (up to >99 : 1 dr) and excellent enantioselectivities (up to >99 % ee ). We also demonstrated that the β ‐amino α ‐substituted tryptamines can be successfully engaged in a further catalytic step, furnishing various α , β ‐substituted tryptamines without erosion of enantioselectivity and with complete diastereoselectivity.