Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 34, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202207008
Keywords
Asymmetric Catalysis; C-H Functionalization; Carbene Insertion; Chiral Diene; Unprotected Indoles
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Funding
- National Natural Science Foundation of China [21672229, 21971103, 21933003, 22193020, 22193023]
- Shenzhen Science and Technology Innovation Commission [JCYJ20200109141408054]
- Guangdong Provincial Key Laboratory of Catalysis [2020B121201002]
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A highly selective C(sp(2))-H functionalization reaction catalyzed by rhodium(I)-diene has been developed, enabling the synthesis of α,β-unsaturated esters containing heteroatoms under mild reaction conditions. Mechanistic studies show that the substrate affects the reaction rate and selectivity.
A rhodium(I)-diene catalyzed highly enantioselective C(sp(2))-H functionalization of simple unprotected indoles, pyrroles, and their common analogues such as furans, thiophenes, and benzofurans with arylvinyldiazoesters has been developed for the first time. This transformation features unusual site-selectivity exclusively at the vinyl terminus of arylvinylcarbene and enables a reliable and rapid synthetic protocol to access a distinctive class of diarylmethine-bearing alpha,beta-unsaturated esters containing a one or two heteroarene-attached tertiary carbon stereocenter in high yields and excellent enantioselectivities under mild reaction conditions. Mechanistic studies and DFT calculations suggest that, compared to the aniline substrate, the more electron-rich indole substrate lowers the C-C addition barrier and alters the rate-determining step to the reductive elimination, leading to different isotope effect.
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