Chen Ya, Pan Yixiao, He Yan-Mei, Fan Qing-Hua
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences (ICCAS), University of Chinese Academy of Sciences, Beijing, 100190, P. R. China.
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, P. R. China.
Angew Chem Int Ed Engl. 2019 Nov 18;58(47):16831-16834. doi: 10.1002/anie.201909919. Epub 2019 Oct 11.
A highly enantioselective iridium- or ruthenium-catalyzed intermolecular reductive amination/asymmetric hydrogenation relay with 2-quinoline aldehydes and aromatic amines has been developed. A broad range of sterically tunable chiral N,N'-diaryl vicinal diamines were obtained in high yields (up to 95 %) with excellent enantioselectivity (up to >99 % ee). The resulting chiral diamines could be readily transformed into sterically hindered chiral N-heterocyclic carbene (NHC) precursors, which are otherwise difficult to access. The usefulness of this synthetic approach was further demonstrated by the successful application of one of the chiral vicinal diamines and chiral NHC ligands in a transition-metal-catalyzed asymmetric Suzuki-Miyaura cross-coupling reaction and asymmetric ring-opening cross-metathesis, respectively.
已开发出一种由铱或钌催化的、与2-喹啉醛和芳香胺进行的高度对映选择性分子间还原胺化/不对称氢化接力反应。以高产率（高达95%）和优异的对映选择性（高达>99% ee）获得了一系列空间可调的手性N,N'-二芳基邻二胺。所得的手性二胺可容易地转化为空间位阻较大的手性N-杂环卡宾（NHC）前体，否则难以获得这些前体。一种手性邻二胺和手性NHC配体分别成功应用于过渡金属催化的不对称铃木-宫浦交叉偶联反应和不对称开环交叉复分解反应，进一步证明了这种合成方法的实用性。
