Efficient β-alkylation of secondary alcohols to α-substituted ketones catalyzed by functionalized Ir complexes via borrowing hydrogen in water,Organic Chemistry Frontiers

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Efficient β-alkylation of secondary alcohols to α-substituted ketones catalyzed by functionalized Ir complexes via borrowing hydrogen in water
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2022-11-22 , DOI: 10.1039/d2qo01541b
Xin Liu _{1,

2} , Wen-Zhe Dong _{1,

2} , Yang Li _{1,

2} , Xiaoqiang Yu ₂ , Wan-Hui Wang _{1,

2} , Yuichiro Himeda ₃ , Ming Bao _{1,

2}

Affiliation

The borrowing hydrogen reaction of alcohols is a green synthetic approach for C–C bond construction, while the selective formation of α-substituted ketones from alcohols in water is highly challenging. Herein, we report an efficient and highly selective β-alkylation of secondary alcohols to α-substituted ketones catalyzed by an amidato Ir(III) complex in water via the borrowing hydrogen strategy. Catalyst 1d bearing a strong electron-donating hydroxyl group on the ligand provided the ketone products with high yields up to 99%. A broad range of substrates, including various aromatic and aliphatic alcohol substrates, were well tolerated under the optimized conditions. Based on control experiments and in situ FT-IR experiments, a plausible mechanism was proposed.

中文翻译：

官能化 Ir 配合物通过在水中借氢催化仲醇高效 β-烷基化为 α-取代酮

醇的借氢反应是构建C-C键的绿色合成方法，而在水中从醇中选择性形成α-取代的酮则极具挑战性。在此，我们报道了一种高效且高选择性的仲醇β-烷基化反应，通过借氢策略在水中由酰胺基 Ir( III ) 络合物催化生成 α-取代酮。在配体上带有强供电子羟基的催化剂1d提供了高达 99% 的高收率的酮产物。广泛的底物，包括各种芳香和脂肪醇底物，在优化条件下具有良好的耐受性。基于控制实验和原位通过 FT-IR 实验，提出了一种似是而非的机制。

更新日期：2022-11-22

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