通过金属-氢化物途径实现非活化脂肪族 C-H 键与炔烃的催化偶联。
Catalytic Coupling between Unactivated Aliphatic C-H Bonds and Alkynes via a Metal-Hydride Pathway.
机构信息
Department of Chemistry, University of Chicago , Chicago, Illinois 60637, United States.
Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2017 Apr 26;139(16):5716-5719. doi: 10.1021/jacs.7b02020. Epub 2017 Apr 12.
We report a Rh(I)-catalyzed site-selective coupling between ketone β-C(sp)-H bonds and aliphatic alkynes using an in situ-installed directing group. Upon hydrogenation or hydration, various β-alkylation or β-aldol products of the ketones are obtained with broad functional group tolerance. Mechanistic investigations support the involvement of a Rh-H intermediate through oxidative addition of Rh(I) into the β-C-H bonds. Thus, to the best of our knowledge, this transformation represents the first example of catalytic couplings between unsaturated hydrocarbons and unactivated aliphatic C-H bonds via a metal-hydride pathway.
我们报告了一种 Rh(I) 催化的酮β-C(sp)-H 键和脂肪族炔烃之间的位点选择性偶联反应，使用了原位安装的导向基团。通过氢化或水合反应，可以得到各种酮的β-烷基化或β-缩醛产物，具有广泛的官能团容忍性。机理研究支持通过 Rh(I) 对β-C-H 键的氧化加成生成 Rh-H 中间体的参与。因此，据我们所知，这种转化代表了通过金属氢化物途径催化不饱和烃和未活化脂肪族 C-H 键之间偶联的首例实例。
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