手性磷酸在铑催化的不对称[2+2+2]环加成反应中的作用：配体、抗衡离子，还是两者皆有？
Chiral Phosphate in Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand, Counterion, or Both?
作者信息
Barbazanges Marion, Caytan Elsa, Lesage Denis, Aubert Corinne, Fensterbank Louis, Gandon Vincent, Ollivier Cyril
机构信息
Sorbonne Universités, UPMC Univ. Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 8232), Case Courrier 229, 4 place Jussieu, 75252, Paris Cedex 05, France.
Institut des Sciences Chimiques de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042, Rennes Cedex, France.
出版信息
Chemistry. 2016 Jun 13;22(25):8553-8. doi: 10.1002/chem.201601188. Epub 2016 May 11.
Investigations based on NMR spectroscopy, mass spectrometry, and DFT calculations shed light on the metallic species generated in the rhodium-catalyzed asymmetric [2+2+2] cycloaddition reaction between diynes and isocyanates with the chiral phosphate TRIP. The catalytic mixture comprising [{Rh(cod)Cl}2 ], 1,4-diphenylphosphinobutane (dppb), and Ag(S)-TRIP actually gives rise to two species, both having an effect on the stereoselectivity. One is a rhodium(I) complex in which TRIP is a weakly coordinating counterion, whereas the other is a bimetallic Rh/Ag complex in which TRIP is a strongly coordinating X-type ligand.
基于核磁共振光谱、质谱和密度泛函理论计算的研究揭示了在铑催化的二炔与异氰酸酯在手性磷酸TRIP存在下的不对称[2+2+2]环加成反应中生成的金属物种。包含[{Rh(cod)Cl}2]、1,4-二苯基膦基丁烷（dppb）和Ag(S)-TRIP的催化混合物实际上产生了两种物种，两者都对立体选择性有影响。一种是铑（I）配合物，其中TRIP是弱配位抗衡离子，而另一种是双金属Rh/Ag配合物，其中TRIP是强配位X型配体。
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