A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions.Key to success is ...A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions.Key to success is photocatalytic generation of tether-tunable distonic radical anions(TDRAs)as proton-coupled electron transfer mediators,enabling polarity-matching-based formation of heteroatom-centered radicals that allows for further controlled exploration of chemical space via C-Cβ-scission.These reactions feature exceptionally broad substrate generality,gram-scale synthesis,potential biocompatibility and late-stage modification of complex molecules,while obviating the use of stoichiometric and often unsafe peroxides in our previous studies.Mechanistic studies support a redox-neutral radical relay pathway enabled by in situ-generated,catalytic TDRAs.展开更多
基金support from the National Natural Science Foundation of China(Nos.22271069,21871067)the Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515012457,2021A1515010190)the Shenzhen Science and Technology Program(Nos.JCYJ20240813105110014 and GXWD20231130100539001).
文摘A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions.Key to success is photocatalytic generation of tether-tunable distonic radical anions(TDRAs)as proton-coupled electron transfer mediators,enabling polarity-matching-based formation of heteroatom-centered radicals that allows for further controlled exploration of chemical space via C-Cβ-scission.These reactions feature exceptionally broad substrate generality,gram-scale synthesis,potential biocompatibility and late-stage modification of complex molecules,while obviating the use of stoichiometric and often unsafe peroxides in our previous studies.Mechanistic studies support a redox-neutral radical relay pathway enabled by in situ-generated,catalytic TDRAs.
