Investigating The Phospholylearbene To Phosphinine Conversion

Phosphinines play a central role in coordination chemistry and homogeneous catalysis, but there are not many synthetic methods by now. In this context, our attention was drawn to the early work of G. Markl describing the conversion of arsolylcarbenes into arsenines. A DFT study suggested that a similar conversion would also work with phospholylcarbenes. We found1-diazoalkylphosphole sulfide4a was converted into phosphinine sulfides4a’whose in situ reduction by triphenylphosphite afforded the dicoordinate phosphinine5a after experiments (Scheme1).Through DFT study, we established the intermediate of the phosphinine sulfides4a’as proposed below, which was obtained by heating compound4a in the presence of methanol as shown below (Scheme2). The stable compound6was got herein and these results validate the calculation of DFT and the reaction mechanism.