gem-Difluoromethylene Alkyne-Enabled Diverse C-H Functionalization and Application to the on-DNA Synthesis of Difluorinated Isocoumarins.
Hui GaoShuang LinShuning ZhangWeijie ChenXiawen LiuGuang YangRichard A LernerHongtao XuZhi ZhouWei YiPublished in: Angewandte Chemie (International ed. in English) (2020)
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 RhIII 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 IrIII -catalyzed system. Mechanistic studies revealed that unusually double β-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.
Keyphrases
- circulating tumor
- cell free
- single molecule
- room temperature
- nucleic acid
- ms ms
- circulating tumor cells
- high glucose
- ionic liquid
- positron emission tomography
- molecular docking
- single cell
- high performance liquid chromatography
- diabetic rats
- tandem mass spectrometry
- mass spectrometry
- climate change
- endothelial cells
- weight loss
- solid phase extraction