Tunable synthesis of chalcophosphinic amides and tertiary phosphinates using tert-butyl N,N-dialkylperoxyamidate

Abstract

The tunable synthesis of chalcophosphinic amides and phosphinates via a copper-catalyzed reaction between phosphine chalcoxides and tert-butyl N,N-dialkylperoxyamidate has been developed. tert-Butyl N,N-dialkylperoxyamidate plays a dual role as a secondary amine and a tertiary alcohol precursor in this transformation, without the need for additional oxidants, bases or other additives. Chalcophosphinic amides were accessed under catalysis with CuI in CH₂Cl₂, while tert-butyl chalcophosphinates were generated with the aid of catalytic Cu(OAc)₂ in THF, which were difficult to obtain by previous methods.