- Visible-light-induced oxidant and metal-free dehydrogenative cascade trifluoromethylation and oxidation of 1,6-enynes with water
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Generally, oxy-trifluoromethylation in olefins is achieved using oxidants and transition metal catalysts. However, labile olefins remain unexplored due to their incompatibility with harsh reaction conditions. Here, unprecedented light-induced oxidant and metal-free tandem radical cyclization-trifluoromethylation and dehydrogenative oxygenation of 1,6-enynes have been achieved using a photoredox catalyst, CF3SO2Na, and phenanthrene-9,10-dione (PQ), Langlois' reagent (CF3SO2Na) and water as the oxygen source. This benign protocol allows for access to various CF3-containing C3-aryloyl/acylated benzofurans, benzothiophenes, and indoles. Moreover, the oxidized undesired products, which are inherently formed by the cleavage of the vinylic carbon and heteroatom bond, have been circumvented under oxidant free conditions. The mechanistic investigations by UV-visible and ESR spectroscopy, electrochemical studies, isotope labelling and density functional theory (DFT) suggest that light induced PQ produced a CF3 radical from CF3SO2Na. The generated CF3 radical adds to the alkene, followed by cyclization, to provide a vinylic radical that transfers an electron to PQ and generates a vinylic cation. Alternatively, electron transfer may occur from the CF3-added alkene moiety, forming a carbocation, which would undergo cationic cyclization to generate a vinylic carbocation. The subsequent addition of water to the vinylic cation, followed by the elimination of hydrogen gas, led to the formation of trifluoromethylated C3-aryloyl/acylated heterocycles.
- Jana, Sadhan,Verma, Ajay,Kadu, Rahul,Kumar, Sangit
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- Ag-Catalyzed Oxidative Cyclization Reaction of 1,6-Enynes and Sodium Sulfinate: Access to Sulfonylated Benzofurans
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A convenient protocol for the synthesis of sulfonylated benzofurans via Ag-catalyzed oxidative cyclization has been established. Chemically stable and easily available sodium sulfinates were used as the sulfonylation reagents and building block for the heterocycle construction. With this novel strategy, various benzofurans bearing dual functional groups could be obtained in good yields with high chemo- and regioselectivities under mild conditions.
- Wu, Wanqing,Yi, Songjian,Huang, Wei,Luo, Di,Jiang, Huanfeng
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- Visible-Light-Induced Cyclization/Aromatization of 2-Vinyloxy Arylalkynes: Synthesis of Thio-Substituted Dibenzofuran Derivatives
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A visible-light-induced cascade reaction of 2-vinyloxy arylalkynes with thiosulfonates was developed and provided unexpected thio-substituted dibenzofuran derivatives in moderate yields. Mechanistic studies revealed the thiosulfonylation product of 2-vinyloxy arylalkyne was the key intermediate, and the additive disulfide played the role of hydrogen abstraction in the aromatization process to offer the desired product. This reaction presents a new reaction mode for the construction of polycyclic oxygen heterocycles.
- Chen, Hui,Chen, Yanyan,Mo, Zuyu,Xu, Yanli,Yan, Yunyun,Zhang, Niuniu
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p. 376 - 381
(2021/01/13)
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- Rhodium-catalyzed intramolecular cyclization of naphthol- or phenol-linked 1,6-enynes through the cleavage and formation of sp2 C-O bonds
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Put a ring on it: A cationic rhodium(I)/binap complex catalyzes the intramolecular cyclization reactions of naphthol- or phenol-linked 1,6-enynes to produce vinylnaphtho- or vinylbenzofurans and vinylnaphtho- or vinylbenzopyrans through the cleavage and f
- Sakiyama, Norifumi,Noguchi, Keiichi,Tanaka, Ken
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supporting information; experimental part
p. 5976 - 5980
(2012/07/03)
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