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

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 CO bonds in a single step.