金属钌配合物催化醇与腈串联反应合成α-取代酰胺

doi:10.6023/cjoc202204039

摘要/Abstract

报道了在90 °C的温和反应条件下, 以Ru-CNN配合物为催化剂, 伯醇和取代苯乙腈为底物, 通过串联反应合成α-烷基酰胺的方法. 该方法具有高的催化活性和选择性, 以及宽泛的底物适应性范围, 都以良好到优秀的收率生成了目标产物, 最高达到96%. 此外, 该一锅反应既不需要添加氧化剂, 也没有副产物, 是绿色、原子经济的酰胺合成方法. 机理研究表明: 首先, 醇无受体脱氢生成醛; 然后, 在碱作用下苯乙腈的α-碳与醛进行亲核加成, 实现C—C偶联并脱水成C=C键; 接着, 醇脱出的氢加成到C=C键成为饱和腈; 最后, 在钌催化剂的作用下亲核加成步骤脱出的水引起氰基水解生成α-取代酰胺.

关键词: 钌配合物, 醇, 无受体脱氢, 酰胺

A ruthenium complex-catalyzed tandem reaction of alcohols with nitriles in one pot has been developed, providing a green and atom-economic synthetic method of α-substituted amide. This method features high reactivity, high selectivity and good substrate compatibility. Good to high yields are obtained for most substrates and the highest yield is 96%. Mechanistic studies reveal that the alcohol first undergoes an acceptorless dehydrogenation into aldehyde. the resulting aldehyde occurs a nucleophilic addition with the α-position carbon of phenylacetonitrile to form α,β-unsaturated nitrile and water. Subsequently, the unsaturated nitrile is hydrogenated with ruthenium-hydride species formed by the dehydrogenation of alcohol to give saturated nitrile, and then the water, generated by the nucleophilic addition, causes the catalytic hydrolysis of cyano group to finally generate α-arylamide.

Key words: ruthenium complex, alcohol, nitrile, α-arylamide

引用此文

王梅, 龚慧华, 付海燕, 郑学丽, 陈华, 李瑞祥. 金属钌配合物催化醇与腈串联反应合成α-取代酰胺[J]. 有机化学, 2022, 42(8): 2418-2427.

Mei Wang, Huihua Gong, Haiyan Fu, Xueli Zheng, Hua Chen, Ruixiang Li. Ruthenium Complex-Catalyzed Tandem Reactions of Alcohols with Acetonitriles for Synthesis of α-Substituted Amides[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2418-2427.

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