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Rhodium‐Catalyzed C−H Activation‐Based Construction of Axially and Centrally Chiral Indenes through Two Discrete Insertions
Author(s) -
Wang Fen,
Jing Jierui,
Zhao Yanliang,
Zhu Xiaohan,
Zhang XuePeng,
Zhao Liujie,
Hu Panjie,
Deng WeiQiao,
Li Xingwei
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202105093
Subject(s) - rhodium , catalysis , chemistry , annulation , steric effects , chirality (physics) , electrophile , axial chirality , stereochemistry , enantioselective synthesis , combinatorial chemistry , organic chemistry , physics , chiral symmetry breaking , nambu–jona lasinio model , quark , quantum mechanics
Reported herein is asymmetric [3+2] annulation of arylnitrones with different classes of alkynes catalyzed by chiral rhodium(III) complexes, with the nitrone acting as an electrophilic directing group. Three classes of chiral indenes/indenones have been effectively constructed, depending on the nature of the substrates. The coupling system features mild reaction conditions, excellent enantioselectivity, and high atom‐economy. In particular, the coupling of N ‐benzylnitrones and different classes of sterically hindered alkynes afforded C−C or C−N atropochiral pentatomic biaryls with a C‐centered point‐chirality in excellent enantio‐ and diastereoselectivity (45 examples, average 95.6 % ee ). These chiral center and axis are disposed in a distal fashion and they are constructed via two distinct migratory insertions that are stereo‐determining and are under catalyst control.