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Chiral Bicyclo[2.2.2]octane‐Fused CpRh Complexes: Synthesis and Potential Use in Asymmetric C−H Activation
Author(s) -
Li Guozhu,
Yan Xiaoqiang,
Jiang Jijun,
Liang Hao,
Zhou Chao,
Wang Jun
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202010489
Subject(s) - cyclopentadienyl complex , rhodium , octane , chemistry , bicyclic molecule , catalysis , yield (engineering) , stereochemistry , ring (chemistry) , asymmetric hydrogenation , enantioselective synthesis , medicinal chemistry , organic chemistry , materials science , metallurgy
A new class of chiral cyclopentadienyl rhodium(I) complexes (CpRh I ) bearing C 2 ‐symmetric chiral bridged‐ring‐fused Cp ligands was prepared. The complexes were successfully applied to the asymmetric C−H activation reaction of N ‐methoxybenzamides with quinones, affording a series of chiral hydrophenanthridinones in up to 82 % yield with up to 99 % ee . Interestingly, structure analysis reveals that the side wall of the optimal chiral CpRh I catalyst is vertically more extended, horizontally less extended, and closer to the metal center in comparison with the classic binaphthyl and spirobiindanyl CpRh I complexes, and may thus account for its superior catalytic performance.