PIDA-Mediated Segment Coupling for the Synthesis of Azidomethyl Substituted Ketones via 1,5-Hydrogen Atom Transfer (HAT) †

Abstract

PIDA-mediated segment coupling of TMSN3, homoallylic alcohol and electron-deficient alkyne/alkene gives γ-azido keto ester/nitrile/phosphonate/sulfones. These metal-free transformations proceed via radical-mediated 1,5-HAT, followed by oxidation, to provide γ-azido keto derivatives with excellent stereoselectivity. This operationally simple three-component coupling involves the formation of C-N, C-C, C-H, and C=O bonds in a single step. Scheme 1. Remote functionalization using azidation of unactivated olefins.