Gold(III)/Sodium Diphenylphosphinobenzene-3-sulfonate (TPPMS) Catalyzed Dehydrative N-Benzylation of Electron-Deficient Anilines in Water
Gold(III)/Sodium Diphenylphosphinobenzene-3-sulfonate (TPPMS) Catalyzed Dehydrative N-Benzylation of Electron-Deficient Anilines in Water
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DOI：
10.1055/s-0037-1611519
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发表时间：
2019-07-01
影响因子：
2.6
通讯作者：
Azumaya, Isao
中科院分区：
文献类型：
--
作者：
Hikawa, Hidemasa;Matsumoto, Mika;Azumaya, Isao
发展了一种缺电子苯胺在水中的脱水N-苄基化反应策略。金(III)/二苯基膦-3-磺酸钠(TPPMS)催化剂是一种高效的Lewis酸，可以在有氧条件下活化醇类。对位取代苯甲醇反应的Hammett研究显示负的Sigma值，表明在决定反应速率的sp(3)C-O键断裂步骤中阳离子电荷积累。溶剂同位素的逆动力学效应(KSIE=0.6)符合特定的酸催化机理。这一简单的方案可以在温和的条件下，在原子经济的过程中执行，不需要碱或其他添加剂，以中等到极好的产率提供缺乏电子的N-苄基苯胺，并以水作为唯一的副产品。
A strategy for the dehydrative N-benzylation of electron-deficient anilines in water has been developed. The gold(III)/sodium diphenylphosphinobenzene-3-sulfonate (TPPMS) catalyst is highly effective as a Lewis acid for the activation of alcohols and tolerates aerobic conditions. A Hammett study in the reaction of para -substituted benzhydryl alcohols shows negative sigma values, indicating a build-up of cationic charge during the rate-determining sp (3) C-O bond-cleavage step. The inverse kinetic solvent isotope effect (KSIE = 0.6) is consistent with a specific acid catalysis mechanism. This simple protocol can be performed under mild conditions in an atom-economic process without the need for base or other additives, furnishing the electron-deficient N -benzylic anilines in moderate to excellent yields along with water as a sole coproduct.