Photoinduced Radical-Ionic Transfer of Various Chlorofluorocarbons to Alkenes from Oxime-Based Surrogates  

作　　者：Jinghui Zhang Muliang Zhang Martin Oestreich 

机构地区：[1]Institut für Chemie,Technische Universität Berlin,10623 Berlin [2]Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry,University of Science and Technology of China,Hefei 230026

出　　处：《CCS Chemistry》2024年第5期1222-1230,共9页中国化学会会刊（英文）

基　　金：by the Alexander von Humboldt Foundation(postdoctoral fellowship to M.Z.,2021-2023);in part by the Deutsche Forschungsgemeinschaft(grant no.Oe 249/26-1)is gratefully acknowledged;M.Z.is also grateful for financial support from the University of Science and Technology of China(grant no.KY9990000197);M.O.is indebted to the Einstein Foundation Berlin for an endowed professorship.

摘　　要：Functional-group-transfer strategies that avoid the use of unsustainable chemicals are attractive for the development of green methodologies.Chlorofluorocarbons(CFCs)not only contribute to the depletion of the stratospheric ozone layer,but their gaseous nature also poses a serious threat in scientific laboratories.Hence,the design of effective and sustainable alternatives to CFCs is highly desirable.Herein,a practical CFC transfer platform for the addition of both a fluoroalkyl group and a chlorine substituent across alkenes by a photomediated redox-neutral manifold using bench-stable and easy-to-handle oxime-based surrogates is reported.The distinct reactivity of these tunable reagents allows for their single-electron reduction to trigger fragmentation driven by benzonitrile formation and loss of carbon dioxide.The other fragments released in that step,namely an electrophilic fluoroalkyl radical and a nucleophilic chloride anion,are subsequently transferred onto alkenes by a radical-ionic mechanism to deliver the desired chlorofluorocarbon products.

关 键 词：ALKENES CHLOROFLUOROCARBONS functionalgroup transfer radical-ionic crossover photoredox catalysis 

分 类 号：O62[理学—有机化学]