Ortho-Trialkylstannyl Arylphosphanes by C-P and C-Sn Bond Formation in Arynes

A novel and efficient approach to ortho‐trialkylstannyl arylphosphanes by the reaction of arynes generated in situ with stannylated phosphanes (R3SnPR2) is described. Concurrent CP and CSn bond formation occurs with high yields, and stannylated products are easily transformed into valuable ortho‐substituted arylphosphanes. The reaction features high efficiency, good regioselectivity, and excellent practicality. Aryne insertion of stannylated phosphanes (R3SnPR2) occurs with high yields under mild conditions. ortho‐Stannylarylphosphanes obtained in this reaction are highly valuable compounds for follow‐up transformations.