铑催化芳基硼酸酯对N-未保护酮亚胺的对映选择性加成：西帕加明的高效合成
Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to N-Unprotected Ketimines: Efficient Synthesis of Cipargamin.
作者信息
Zhu Jinbin, Huang Linwei, Dong Wei, Li Naikai, Yu Xingxin, Deng Wei-Ping, Tang Wenjun
机构信息
Shanghai Key Laboratory of New Drug Design, School of Pharmacy, East China University of Science and Technology, 130 Mei Long Rd, Shanghai, 200237, China.
State Key Laboratory of Bio-Organic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Rd, Shanghai, 200032, China.
出版信息
Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16119-16123. doi: 10.1002/anie.201910008. Epub 2019 Sep 24.
Highly enantioselective rhodium-catalyzed addition of arylboroxines to N-unprotected ketimines is realized for the first time by employing chiral BIBOP-type ligands with a Rh loading as low as 1 mol %. A range of chiral α-trifluoromethyl-α,α-diaryl α-tertiary amines or 3-amino-3-aryloxindoles were formed with excellent ee values and yields by employing either WingPhos or PFBO-BIBOP as the ligand. The method has enabled an efficient enantioselective synthesis of cipargamin.
首次通过使用手性BIBOP型配体，以低至1 mol%的铑负载量实现了铑催化芳基硼酸酯对N-未保护酮亚胺的高度对映选择性加成。通过使用WingPhos或PFBO-BIBOP作为配体，一系列手性α-三氟甲基-α,α-二芳基叔胺或3-氨基-3-芳基氧化吲哚以优异的对映体过量值和产率得以形成。该方法实现了西帕加明的高效对映选择性合成。
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