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Revisiting the CuII-Catalyzed Asymmetric Friedel-Crafts Reaction of Indole with Trifluoropyruvate
Thien Phuc Le1, Kazuyuki Higashita1, Shinji Tanaka1
1Graduate School of Pharmaceutical Sciences and Research Center for Materials Science , Nagoya University , Chikusa, Nagoya 464-8601 , Japan.
Abstract:
A CuII complex of bisamidine ligand L S catalyzes the Friedel-Crafts (FC) reaction of indole with trifluoropyruvate with high generality, yielding the highly enantiomerically enriched FC adduct. Electron-rich indoles have high reactivity due to a dual activation mechanism showing second-order kinetics for CuII, whereas indoles with a soft substituent at C(4) proceed at a rate that is three orders of magnitude lower via a coordination mechanism, which reverses the sense of enantioselectivity.
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