Metal-Free Intramolecular Aminophosphination of Allenes

Abstract

A metal-free intramolecular aminophosphination of sulfonamidoallenes with diarylphosphine oxides and Tf2O was developed. This method offers a general and practical procedure to construct valuable alkenylphosphine-substituted N-heterocycles via the bifunctionalization reaction of allenes in good yields under mild conditions.

Regio- and stereoselective access to highly substituted vinylphosphine oxides via metal-free electrophilic phosphonoiodination of alkynes

“…Quaternary phosphirenium salts (QPrS), which could be easily generated from alkynes and secondary phosphine oxides in the presence of Tf 2 O, are also considered to be powerful intermediates for the construction of organophosphorus compounds [36][37][38][39][40][41][42] . However, in contrast to epoxides [43][44][45][46][47] and aziridines [48][49][50][51] , the phosphorus atom possesses inherent electrophilicity, resulting from the polarity inversion of the C-P bond 52 , which leads to C-addition occurring exclusively when a weakly nucleophilic reagent attacks the ring [53][54][55] (Fig. 1a).…”