Reactivity of a Sterically Unencumbered α-Borylated Phosphorus Ylide towards Small Molecules.

The influence of substituents on α-borylated phosphorus ylides (α-BCPs) has been investigated in a combined experimental and quantum chemical approach. The synthesis and characterization of Me PC(H)B(iBu) (1), consisting of small Me substituents on phosphorous and iBu residues on boron, is reported. Compound 1 is accessible through a novel synthetic approach, which has been further elucidated through DFT studies. The reactivity of 1 towards various small molecules was probed and compared with that of a previously published derivative, Ph PC(Me)BEt (2). Both α-BCPs react with NH to undergo heterolytic N-H bond cleavage. Different di- and trimeric ring structures were observed in the reaction products of 1 with CO and CO . With PhNCO and PHNCS, the expected insertion products [Me PC(H)(PhNCO)B(iBu) ] and [Me PC(H)(PhNCS)B(iBu) ], respectively, were isolated.