Synthesis and Reactivity of a Zinc Diazoalkyl Complex: [3+2] Cycloaddition Reaction with Carbon Monoxide
Shengjie Jiang, Yanping Cai, Thayalan Rajeshkumar, Iker Del Rosal, Laurent Maron, Xin Xu
Abstract
Abstract This work reports the synthesis, characterization, and reactivity of the first example of a well‐defined zinc α‐diazoalkyl complex. Treatment of zinc(I)‐zinc(I) bonded compound L 2 Zn 2 [ L =CH 3 C(2,6‐ i Pr 2 C 6 H 3 N)CHC(CH 3 )(NCH 2 CH 2 PPh 2 )] or zinc(II) hydride L ZnH with trimethylsilyldiazomethane affords zinc diazoalkyl complex L ZnC(N 2 )SiMe 3 . This complex liberates N 2 in the presence of a nickel catalyst to form an α‐zincated phosphorus ylide by reacting with the pendant phosphine. It selectively undergoes formal [3+2] cycloaddition with CO 2 or CO to form the corresponding product with a five‐membered heterocyclic core. Notably, the use of CO in such a [3+2] cycloaddition reaction is unprecedented, reflecting a novel CO reaction mode.