Ruthenium Pybox-Catalyzed Enantioselective Intramolecular C-H Amination of Sulfamoyl Azides en Route to Chiral Vicinal Diamines.

Abstract

Enantioselective C(sp3)-H aminations allow an efficient access to nonracemic chiral amines. This work reports the catalytic asymmetric synthesis of chiral 1,2,5-thiadiazolidine-1,1-dioxides by an enantioselective ring-closing 1,5-C-H amination of sulfamoyl azides. The reaction is catalyzed by a recently introduced simple chiral ruthenium bis(oxazoline) (pybox) complex ( Angew. Chem. Int. Ed. 2020, 59, 12395) and provides cyclic 5-membered sulfamide products in up to 98% yield and up to 98% ee if the C-H bond is in a benzylic position. Mechanistic experiments support a stepwise mechanism in which an intermediate ruthenium nitrenoid species initiates a 1,5-hydrogen atom transfer followed by an immediate radical rebound. The cyclic sulfamide products are suitable intermediates for the synthesis of chiral vicinal diamines as has been verified for a representative example.