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双功能钌配合物催化的串联C-C键形成:以醇作为烷基化试剂的高效且原子经济的策略

Bifunctional Ru -Complex-Catalysed Tandem C-C Bond Formation: Efficient and Atom Economical Strategy for the Utilisation of Alcohols as Alkylating Agents.

作者信息

Roy Bivas Chandra, Chakrabarti Kaushik, Shee Sujan, Paul Subhadeep, Kundu Sabuj

机构信息

Department of Chemistry, IIT Kanpur, Kanpur, 208016, UP, India.

出版信息

Chemistry. 2016 Dec 12;22(50):18147-18155. doi: 10.1002/chem.201603557. Epub 2016 Oct 31.

Abstract

Catalytic activities of a series of functional bipyridine-based Ru complexes in β-alkylation of secondary alcohols using primary alcohols were investigated. Bifunctional Ru complex (3 a) bearing 6,6'-dihydroxy-2,2'-bipyridine (6DHBP) ligand exhibited the highest catalytic activity for this reaction. Using significantly lower catalyst loading (0.1 mol %) dehydrogenative carbon-carbon bond formation between numerous aromatic, aliphatic and heteroatom substituted alcohols were achieved with high selectivity. Notably, for the synthesis of β-alkylated secondary alcohols this protocol is a rare one-pot strategy using a metal-ligand cooperative Ru system. Remarkably, complex 3 a demonstrated the highest reactivity compared to all the reported transition metal complexes in this reaction.

摘要

研究了一系列基于联吡啶的功能性钌配合物在伯醇对仲醇进行β-烷基化反应中的催化活性。带有6,6'-二羟基-2,2'-联吡啶(6DHBP)配体的双功能钌配合物(3 a)对该反应表现出最高的催化活性。使用显著更低的催化剂负载量(0.1 mol %),在众多芳香族、脂肪族和杂原子取代的醇之间实现了具有高选择性的脱氢碳-碳键形成。值得注意的是,对于β-烷基化仲醇的合成,该方法是一种罕见的使用金属-配体协同钌体系的一锅法策略。值得注意的是,与该反应中所有已报道的过渡金属配合物相比,配合物3 a表现出最高的反应活性。

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