- Divergent Photocatalytic Reactions of α-Ketoesters under Triplet Sensitization and Photoredox Conditions
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The long-lived triplet excited states of transition metal photocatalysts can activate organic substrates via either energy- or electron-transfer pathways, and the rates of these processes can be influenced by rational tuning of the reaction conditions. The characteristic reactive intermediates generated, however, are distinct and can exhibit very different reactivity patterns. This mechanistic diversity available to photocatalytic reactions might thus offer an opportunity to engineer divergent reactions that give markedly different chemical outcomes under superficially similar conditions. Herein, we show that the photocatalytic reactions of benzoylformate esters with alkenes can be directed toward either Paternò-Büchi cycloadditions or allylic functionalization reactions under conditions favoring energy transfer or electron transfer, respectively. These studies provide a framework for designing other divergent photocatalytic methods that produce different sets of reaction outcomes under photoredox and triplet sensitization conditions.
- Dong, Xiao,Yoon, Tehshik P.,Zheng, Jian
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supporting information
(2020/09/02)
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- ESTER COMPOUND AND MEDICINAL USE THEREOF
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A novel therapeutic agent for hyperlipidemia, which is an ester compound represented by the formula (1") (wherein ???R1 and R2 are each hydrogen atom or optionally substituted aryl, etc.; ???X is -COO- or -CON(R10)-; ???R3 and R4 are each hydrogen atom, C1-C6 alkyl or C1-C6 alkoxy, etc.; ???R5, R6 and R7 are each hydrogen atom, C1-C6 alkyl or C1-C6 alkoxy, etc.; ???R8 and R9 are each independently hydrogen atom, C1-C6 alkyl, -CON(R18)(R19) or -COO(R20), etc.; ???ring A, ring B and ring C are each independently aryl or heterocycle residue, etc.; ???Alk1 and Alk2 are each independently alkanediyl, etc.; ???l and m are each an integer of 0 or 1 to 3) or a prodrug thereof, or a pharmaceutically acceptable salt of either. The therapeutic agent selectively inhibits MTP in the small intestine, thus causes no such side effect as a fatty liver.
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