Synthesis and Reactivity of a Zinc Diazoalkyl Complex: [3+2] Cycloaddition Reaction with Carbon Monoxide |
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| Authors: | Dr. Shengjie Jiang Yanping Cai Thayalan Rajeshkumar Iker del Rosal Prof. Dr. Laurent Maron Prof. Dr. Xin Xu |
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| Affiliation: | 1. Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123 P. R. China;2. LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse, France |
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| 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 2Zn2 [ L =CH3C(2,6-iPr2C6H3N)CHC(CH3)(NCH2CH2PPh2)] or zinc(II) hydride L ZnH with trimethylsilyldiazomethane affords zinc diazoalkyl complex L ZnC(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. |
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| Keywords: | CO Activation Cycloaddition DFT Calculation Diazo Compounds Zinc |
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