Chiral Bicyclic NHC/Rh Complexes and Their Application to Catalytic Asymmetric Ring-Opening Reaction of Oxabenzonorbornadienes with Amines
Chiral Bicyclic NHC/Rh Complexes and Their Application to Catalytic Asymmetric Ring-Opening Reaction of Oxabenzonorbornadienes with Amines
复制标题
手性双环NHC/Rh配合物及其在催化氧苯并降冰片二烯与胺不对称开环反应中的应用
DOI：
10.1021/acs.joc.1c02836
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Yoshida Kazuhiro
中科院分区：
文献类型：
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作者：
Seki Mizuki;Yoshida Kazuhiro
合成了一种带有手性双环NHC配体[RhCl（3az）（cod）]4az的铑配合物，并通过X射线衍射分析、高分辨质谱和多核核磁共振谱对其进行了表征。用CO取代4az的COD配体，合成了双羰基配合物[RhCl（3az）（CO）2]5az，通过红外光谱和X射线衍射分析研究了3az的电子结构和空间位阻性质，考察了4az作为手性催化剂在Rh催化的氧杂苯并降冰片二烯与胺的不对称开环反应中的应用潜力，并且以良好的产率和良好的对映选择性（高达81%ee）得到相应的产物。
A rhodium complex bearing a chiral bicyclic NHC ligand, [RhCl(3az)(cod)]4az, was synthesized and fully characterized by X-ray diffraction analysis, high-resolution mass spectrometry, and multinuclear NMR spectroscopy. The electronic and steric properties of NHC ligand3azwere evaluated by IR measurement and X-ray diffraction analysis of dicarbonyl complex [RhCl(3az)(CO)2]5az, which was prepared by replacing the COD ligand of4azwith CO. The potential of novel complex4azas a chiral catalyst was investigated in the Rh-catalyzed asymmetric ring-opening reaction of oxabenzonorbornadienes with amines, and the corresponding products were afforded in good yields with good enantioselectivities (up to 81% ee).