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A unified photoredox-catalysis strategy for C(sp3)–H hydroxylation and amidation using hypervalent iodine
Chemical Science ( IF 8.4 ) Pub Date : 2017-09-04 00:00:00 , DOI: 10.1039/c7sc02773g
Guo-Xing Li 1, 2, 3, 4, 5 , Cristian A. Morales-Rivera 6, 7, 8, 9 , Fang Gao 1, 2, 3, 4, 5 , Yaxin Wang 1, 2, 3, 4, 5 , Gang He 1, 2, 3, 4, 5 , Peng Liu 6, 7, 8, 9 , Gong Chen 1, 2, 3, 4, 5
Affiliation  

We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C–H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl–OH) oxidant is critical for efficient tertiary C–H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C–H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl–OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by H2O or CH3CN cosolvent is presented.

中文翻译:

使用高价碘的C(sp 3)-H羟基化和酰胺化的统一光氧化还原催化策略

我们报告了统一的光氧化还原催化策略,用于叔和苄基C–H键的羟基化和酰胺化。羟基全氟苯并吲哚酚(PFB1-OH)氧化剂的使用对于有效的叔C-H官能化至关重要,这可能是由于苯并吲哚酚基团的亲电性增强所致。在相似的条件下,可以使用未改性的羟基苯并恶二酚氧化剂Bl-OH将苄基亚甲基CH键进行羟基化或酰胺化反应。提出了一种离子机制,涉及通过H 2 O或CH 3 CN助溶剂对碳正离子中间体的亲核捕集。
更新日期:2017-09-25
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