Visible-Light-Triggered Monofluoromethylation of Alkenes by Strongly Reducing 1,4-Bis(diphenylamino)naphthalene Photoredox Catalysis
Visible-Light-Triggered Monofluoromethylation of Alkenes by Strongly Reducing 1,4-Bis(diphenylamino)naphthalene Photoredox Catalysis
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DOI：
10.1021/acscatal.9b00473
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发表时间：
2019-04
期刊：
影响因子：
12.9
通讯作者：
Naoki Noto;T. Koike;M. Akita
中科院分区：
文献类型：
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作者：
Naoki Noto;T. Koike;M. Akita
利用可见光无金属光氧化还原催化作用，以亚砜亚胺为前体（CH_2F-S（=O）（=NTs）-Ph），与易得的1，4-双（二苯胺基）萘反应，可以很容易地生成单氟甲基（CH_2F）自由基。基于高激发能（E0，0）和发色团间共轭的催化剂设计具有强还原能力和高量子产率的光催化剂的发射。此外，它们的物理化学性质在各种极性溶剂中保持不变。本发明的体系适合于具有高官能团耐受性的烯烃的氧-单氟甲基化，即，从各种烯烃一步合成γ-氟代醇支架。还示出了潜在生物活性分子的后期功能化的应用。
Monofluoromethyl (CH2F) radical can be easily generated from a sulfoximine-based precursor (CH2F–S(=O)(=NTs)-Ph) by the action of visible-light metal-free photoredox catalysis with readily accessible 1,4-bis(diphenylamino)naphthalene. The catalyst design based on the high excitation energy (E0,0) and interchromophoric conjugation features a strong reducing power and a high quantum yield of emission of the photocatalyst. In addition, their photophysical properties are preserved in various polar solvents. The present system is amenable to oxy-monofluoromethylation of alkenes with high functional-group tolerance, i.e., single-step synthesis of γ-fluoroalcohol scaffolds from various alkenes. Applications to late-stage functionalization of potentially bioactive molecules are also shown.