Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 4, Pages 1959-1966Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202013052
Keywords
C− H functionalization; chemodivergence; DNA-encoded libraries; gem-difluoromethylene alkynes; Rh; Ir catalysis
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Funding
- NSFC [21877020, U19A2011]
- Guangdong Natural Science Funds for Distinguished Young Scholar [2017A030306031]
- Natural Science Foundation of Guangdong Province [2018A030313274, 2019A1515010935]
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This study reports unprecedented diverse C-H activation/[4+2] annulations of simple benzoic acids using gem-difluoromethylene alkynes as effectors. The outcomes of the chemodivergent reaction are well-tuned by Rh/Ir-catalyzed system, resulting in different skeletons depending on the solvent used. Mechanistic studies reveal the involvement of double beta-F eliminations and fluorine effect-induced regioselective reductive eliminations in enabling distinct reaction modes for divergent product formations.
Using gem-difluoromethylene alkynes as effectors, unprecedented diverse C-H activation/[4+2] annulations of simple benzoic acids are reported. The chemodivergent reaction outcomes are well-tuned by Rh/Ir-catalyzed system; in the Rh-III catalysis, 3-alkenyl-1H-isochromen-1-one and 3,4-dialkylideneisochroman-1-one skeletons are afforded in a solvent-dependent manner whereas difluoromethylene-substituted 1H-isochromen-1-ones are generated under the Ir-III-catalyzed system. Mechanistic studies revealed that unusually double beta-F eliminations and fluorine effect-induced regioselective reductive elimination are independently involved to enable distinct reaction modes for divergent product formations. Besides, synthetic application in both the derivatization of obtained diene products and the on-DNA synthesis of DNA-tagged difluorinated isocoumarin have been demonstrated, which manifested great potential for synthetic utility of the developed protocols.
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