UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego , La Jolla, California 92093-0358, United States.
J Am Chem Soc. 2016 Jun 29;138(25):7884-7. doi: 10.1021/jacs.6b05221. Epub 2016 Jun 20.
A versatile methodology, involving readily available starting materials, allows for the synthesis of stable hemilabile bidentate cyclic (alkyl)(amino)carbenes (CAACs) featuring alkene, ether, amine, imine, and phosphine functionalities. The stability of the free carbenes has been exploited for the synthesis of copper(I) and gold(I) complexes. It is shown that the pendant imine moiety stabilizes the gold(III) oxidation state and enables the C-C bond oxidative addition of biphenylene to the corresponding cationic gold(I) complex. The latter and the corresponding copper(I) complex show high catalytic activity for the hydroarylation of α-methylstyrene with N,N-dimethylaniline, and the copper(I) complex promotes the anti-Markovnikov hydrohydrazination of phenyl acetylene with high selectivity.
一种通用的方法，涉及到易得的起始原料，可以合成稳定的缺电子双齿环状（烷基）（氨基）卡宾（CAACs），其具有烯烃、醚、胺、亚胺和膦官能团。游离卡宾的稳定性已被用于合成铜（I）和金（I）配合物。结果表明，侧链亚胺部分稳定了金（III）的氧化态，并使联苯的 C-C 键加成到相应的阳离子金（I）配合物。后者和相应的铜（I）配合物对α-甲基苯乙烯与 N，N-二甲基苯胺的氢芳基化反应具有很高的催化活性，而铜（I）配合物则以高选择性促进苯乙炔的反马氏规则氢肼化反应。
