N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes
N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes
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DOI：
10.1021/jacs.9b00880
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发表时间：
2019-03-06
影响因子：
15
通讯作者：
Ohmiya, Hirohisa
中科院分区：
文献类型：
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作者：
Ishii, Takuya;Kakeno, Yuki;Ohmiya, Hirohisa
我们发现，N-杂环卡宾催化促进了前所未有的脱羧偶联芳基醛和叔或仲烷基羧酸衍生的氧化还原活性酯，以产生芳基烷基酮。反应条件温和，不含过渡金属，是该方法的特点。通过对药物和天然产物的功能化，证明了该方案的能力。一个反应途径，涉及单电子转移从烯醇化形式的Breslow中间体的氧化还原酯，然后重组所产生的自由基对，形成碳-碳键的建议。
We found that N-heterocyclic carbene catalysis promoted the unprecedented decarboxylative coupling of aryl aldehydes and tertiary or secondary alkyl carboxylic acid-derived redox-active esters to produce aryl alkyl ketones. The mild and transition-metal-free reaction conditions are attractive features of this method. The power of this protocol was demonstrated by the functionalization of pharmaceutical drugs and natural product. A reaction pathway involving single electron transfer from an enolate form of Breslow intermediate to a redox ester followed by recombination of the resultant radical pair to form a carbon-carbon bond is proposed.