PIDA-mediated segment coupling for the synthesis of azido-methyl substituted ketones via 1,5-hydrogen atom transfer (HAT)

Abstract

PIDA-mediated segment coupling of TMSN₃, a homoallylic alcohol and an 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 CO bonds in a single step.