Synthesis and Reactivity of a Zinc Diazoalkyl Complex: [3+2] Cycloaddition Reaction with Carbon Monoxide
Jiang Shengjie1, Cai Yanping1, Rajeshkumar Thayalan2, del Rosal Iker2, Maron Laurent2* , Xu Xin1*（徐信）
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (P. R. China)
2LPCNO, CNRS & INSA, Université Paul Sabatier 135 Avenuede Rangueil, 31077 Toulouse (France)
Angew. Chem. Int. Ed. 2023, e202307244
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 L2Zn2 [L=CH3C(2,6-iPr2C6H3N)CHC(CH3)(NCH2CH2PPh2)] or zinc(II) hydride LZnH with trimethylsilyldiazomethane affords zinc diazoalkyl complex LZnC(N2)SiMe3. This complex liberates N2 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 CO2 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.
链接：//onlinelibrary.wiley.com/doi/10.1002/anie.202307244
