2‐Hydroperfluoropropyl azide—a versatile reagent for the oxidative fluorination of organic compounds of trivalent phosphorus

Abstract

ABSTRACT

Synthesis, Stability and Reactivity of α‐Fluorinated Azidoalkanes

“…[43] The general schemeo fr eaction of fluoroalkylated azides with P III compounds is depicted in Scheme 33. [8,13,[44][45][46][47] Initially,p hosphazides form. They are generally unstable and decompose to iminophosphoranes.…”

“…When (R 2 N) 3 Pa re used, the phosphazides are stable and can be isolated. [46,47] Eventually, P V products form as ar esult of oxidative fluorination.…”

“…Soon after Makarov's first synthesis of azidotrifluoromethane, a variant of Staudinger reaction with phosphorus(III) compounds was reported in which stable N‐trifluoromethyl iminophosphoranes were isolated (Scheme ) . The general scheme of reaction of fluoroalkylated azides with P III compounds is depicted in Scheme . Initially, phosphazides form.…”

“…They are generally unstable and decompose to iminophosphoranes. When (R 2 N) 3 P are used, the phosphazides are stable and can be isolated . Eventually, P V products form as a result of oxidative fluorination.…”

Reactions of α-difluoro azides with olefins

“…To confirm the 2 exo 7 syn configuration, the signal of H(7) should unambiguously be assigned, separately from H(1) and H (4). The COSY spectrum shows cross peaks for H(1) and H(4) coupled with H(2) and H(3), the latter two being unambiguously assigned from the 1D spectrum; such cross peaks for H (7) are absent.…”