Control of Site-Selectivity in Hydrogen Atom Transfer by Electrostatic Interaction: Proximal-Selective C(sp3)-H Alkylation of 2-Methylanilinium Salts Using a Decatungstate Photocatalyst
Control of Site-Selectivity in Hydrogen Atom Transfer by Electrostatic Interaction: Proximal-Selective C(sp3)-H Alkylation of 2-Methylanilinium Salts Using a Decatungstate Photocatalyst
复制标题
通过静电相互作用控制氢原子转移的位点选择性：使用十钨酸盐光催化剂对 2-甲基苯胺盐进行近端选择性 C(sp3)-H 烷基化
作者：
Zeng;J.; Torigoe;T.; Kuninobu;Y.
研究了2-甲基苯胺盐通过自由基中间体的C(SP3)-H位选择性烷基化反应。阴离子十钨酸光催化剂([W10O32]4-)通过静电作用与底物的氨基相互作用，并在紫外光照射下选择性地从近端的苄基碳原子中提取氢原子。各种2-甲基苯胺盐与缺电子的烯烃反应。烷基化产物通过C-N键的裂解和四氢苯并氮杂环酮衍生物的分子内环化，成功地转化为芳基碘。机理研究清楚地表明，[W10O32]4-与氨基之间存在相互作用。
Site-selective C(sp3)–H alkylation of 2-methylanilinium salts via radical intermediates was developed. The anionic decatungstate photocatalyst ([W10O32]4–) interacts with the ammonium group of the substrate through electrostatic interaction and selectively abstracts a hydrogen atom from the proximal benzylic carbon atom under UV irradiation. A variety of 2-methylanilinium salts reacted with electron-deficient alkenes. The alkylated product was successfully converted into an aryl iodide via cleavage of the C–N bond and a tetrahydrobenzoazepinone derivative by intramolecular cyclization. Mechanistic studies clearly show the existence of the interactions between [W10O32]4–and the ammonium group.