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241.
Carlos R. Azpilcueta-Nicolas Derek Meng Simon Edelmann Jean-Philip Lumb 《Angewandte Chemie (International ed. in English)》2023,62(6):e202215422
Dearomatization reactions involving radical cyclizations can facilitate the synthesis of complex polycyclic systems that find applications in medicinal chemistry and natural product synthesis. Here we employ redox-neutral photocatalysis to affect a radical spirocyclization that transforms biaryls into spirocyclic cyclohexadienones under mild reaction conditions. In a departure from previously reported methods, our work demonstrates the polarity mismatched addition of a nucleophilic radical to an electron rich arene, and allows the regioselective synthesis of 2,4- or 2,5-cyclohexadienones with broad functional group tolerance. By transforming biaryls into spirocycles, our methodology accesses underexplored three-dimensional chemical space, and provides an efficient means of creating quaternary spirocenters that we apply to the first synthesis of the cytotoxic plant metabolite denobilone A. 相似文献
242.
Yen-Chu Lu Prof. Julian G. West 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202213055
Decarboxylative protonation is a general deletion tactic to replace polar carboxylic acid groups with hydrogen or its isotope. Current methods rely on the pre-activation of acids, non-sustainable hydrogen sources, and/or expensive/highly oxidizing photocatalysts, presenting challenges to their wide adoption. Here we show that a cooperative iron/thiol catalyst system can readily achieve this transformation, hydrodecarboxylating a wide range of activated and unactivated carboxylic acids and overcoming scope limitations in previous direct methods. The reaction is readily scaled in batch configuration and can be directly performed in deuterated solvent to afford high yields of d-incorporated products with excellent isotope incorporation efficiency; characteristics not attainable in previous photocatalyzed approaches. Preliminary mechanistic studies indicate a radical mechanism and kinetic results of unactivated acids (KIE=1) are consistent with a light-limited reaction. 相似文献
243.
Zeyu Feng Lucas Riemann Zichen Guo David Herrero Martin Simon Dr. Christopher Golz Prof. Dr. Ricardo A. Mata Prof. Dr. Manuel Alcarazo 《Angewandte Chemie (International ed. in English)》2023,62(35):e202306764
The evaluation of the pentafluorocyclopropyl group as a chemotype in crop protection and medicinal chemistry has been hampered in the past by the lack of suitable methodologies that enable the practical incorporation of this moiety into advanced synthetic intermediates. Herein, we report the gram-scale synthesis of an unprecedented sulfonium salt, 5-(pentafluorocyclopropyl)dibenzothiophenium triflate, and its use as a versatile reagent for the photoinduced C−H pentafluorocyclopropylation of a broad series of non-previously functionalized (hetero)arenes through a radical mediated mechanism. The scope and potential benefits of the protocol developed are further demonstrated by the late-stage introduction of the pentafluorocyclopropyl unit into biologically relevant molecules and widely used pharmaceuticals. 相似文献