This publication is part of a Special Collection on "Phosphorus in Catalysis". Please check the ChemCatChem homepage for more articles in the collection. Scheme 1. Structural units for the engineering of photoresponsive trivalent phosphines: (a) azobenzenes, (b) dithienylethenes, (c) biindanes.

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.