Luo Yan, Huang Guanglong, Ding Kuiling, Xue Xiao-Song, Wang Xiaoming
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, China.
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, China.
Nat Chem. 2025 Jun 13. doi: 10.1038/s41557-025-01834-8.
The carbonyl group is one of the most important functional groups in organic chemistry. C=O cleavage and full transfer of the resulting fragments into final products would be extremely attractive and open up new avenues in retrosynthetic planning. In this context, as an N-containing carbonyl compound, the transformations of formamides, wherein C=O cleavage occurring with simultaneous incorporation of 'O' and aminomethine moieties to highly functionalized amines, remain a formidable challenge. Here we disclosed a dirhodium/Xantphos or dirhodium-palladium dual catalysed reaction of diazo compounds and allylic substrates in dimethyl formamide, giving various α-aminoketones and cyclopentenone derivatives efficiently featured with extensively reorganized structure, wherein a carbenic carbon was formally inserted into C=O bond and α-group of the carbene was shifted to the residual aminomethine moiety. Mechanistic studies revealed that three or six domino steps are involved in this catalytic process, including epoxidation, dyotropic type rearrangement, allylic alkylation, Claisen rearrangement, isomerization and Nazarov cyclization.
羰基是有机化学中最重要的官能团之一。C=O键的断裂以及由此产生的片段完全转化为最终产物将极具吸引力，并为逆合成规划开辟新途径。在此背景下，作为一种含氮羰基化合物，甲酰胺的转化，即C=O键断裂同时将“O”和氨基次甲基部分引入到高度官能化的胺中，仍然是一个巨大的挑战。在此，我们报道了一种在二甲基甲酰胺中，重氮化合物与烯丙基底物的双铑/Xantphos或双铑 - 钯双催化反应，能高效地生成各种结构广泛重组的α - 氨基酮和环戊烯酮衍生物，其中一个碳烯碳正式插入到C=O键中，并且卡宾的α - 基团转移到残留的氨基次甲基部分。机理研究表明，该催化过程涉及三个或六个多米诺步骤，包括环氧化、双烯丙基重排、烯丙基烷基化、克莱森重排、异构化和纳扎罗夫环化。
