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A General Strategy for Aliphatic C–H Functionalization Enabled by Organic Photoredox Catalysis
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2018-03-09 , DOI: 10.1021/jacs.8b00592
Kaila A. Margrey 1 , William L. Czaplyski 1 , David A. Nicewicz 1 , Erik J. Alexanian 1
Affiliation  

Synthetic transformations that functionalize unactivated aliphatic C-H bonds in an intermolecular fashion offer unique strategies for the synthesis and late-stage derivatization of complex molecules. Herein we report a general approach to the intermolecular functionalization of aliphatic C-H bonds using an acridinium photoredox catalyst and phosphate salt under blue LED irradiation. This strategy encompasses a range of valuable C-H transformations, including the direct conversions of a C-H bond to C-N, C-F, C-Br, C-Cl, C-S, and C-C bonds, in all cases using the alkane substrate as the limiting reagent. Detailed mechanistic studies are consistent with the intermediacy of a putative oxygen-centered radical as the hydrogen atom-abstracting species in these processes.

中文翻译:

通过有机光氧化还原催化实现脂肪族 C-H 功能化的一般策略

以分子间方式功能化未活化脂肪族 CH 键的合成转化为复杂分子的合成和后期衍生化提供了独特的策略。在此,我们报告了在蓝光 LED 照射下使用吖啶光氧化还原催化剂和磷酸盐对脂肪族 CH 键进行分子间官能化的一般方法。该策略包括一系列有价值的 CH 转化,包括将 CH 键直接转化为 CN、CF、C-Br、C-Cl、CS 和 CC 键,在所有情况下都使用烷烃底物作为限制试剂。详细的机理研究与假定的以氧为中心的自由基作为这些过程中的氢原子提取物质的中介是一致的。
更新日期:2018-03-09
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