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高效钳形锌催化仲醇/酮与伯醇的均相α-烷基化反应及Friedländer喹啉合成反应。

Potent pincer-zinc catalyzed homogeneous α-alkylation and Friedländer quinoline synthesis reaction of secondary alcohols/ketones with primary alcohols.

作者信息

Jana Debashis, Roy Sima, Naskar Srijita, Halder Supriyo, Kanrar Gopal, Pramanik Kausikisankar

机构信息

Department of Chemistry, Jadavpur University, Kolkata 700032, India.

Department of Chemistry, St. Xavier's College (Autonomous), Kolkata-700016, India.

出版信息

Org Biomol Chem. 2024 Aug 7;22(31):6393-6408. doi: 10.1039/d4ob00988f.

Abstract

Herein, we describe an air- and moisture-stable, homogeneous zinc catalyst stabilised using an electron deficient N^N^N pincer-type ligand. This ternary, penta-coordinated neutral molecular catalyst [Zn(N^N^N)Cl] selectively produces α-alkylated ketone derivatives (14 examples) through a one-pot acceptorless dehydrogenative coupling (ADC) reaction between secondary and primary alcohols using the borrowing hydrogen (BH) approach in good to excellent isolated yields (up to 93%). It is worth noting that this catalyst also provides an eco-friendly route for the synthesis of quinoline derivatives (30 examples) using 2-aminobenzyl alcohols as alkylating agents successive dehydrogenative coupling and N-annulation reactions. This cost effective, easy to synthesize and environmentally benign catalyst shows excellent stability in catalytic cycles under open-air conditions, as evident from its high turnover number (∼10), and is activated by using a catalytic amount of base under milder conditions.

摘要

在此,我们描述了一种使用缺电子的N^N^N钳型配体稳定的、对空气和湿气稳定的均相锌催化剂。这种三元五配位中性分子催化剂[Zn(N^N^N)Cl]通过借氢(BH)方法,在仲醇和伯醇之间进行一锅无受体脱氢偶联(ADC)反应,选择性地生成α-烷基化酮衍生物(14个实例),分离产率良好至优异(高达93%)。值得注意的是,该催化剂还提供了一条环保路线,以2-氨基苄醇作为烷基化剂,通过连续的脱氢偶联和N-环化反应合成喹啉衍生物(30个实例)。这种成本效益高、易于合成且环境友好的催化剂在露天条件下的催化循环中表现出优异的稳定性,其高周转数(约10)证明了这一点,并且在较温和的条件下使用催化量的碱即可活化。

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