Cao Jing, Schull Cullen R, Scheidt Karl A
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA.
Angew Chem Int Ed Engl. 2025 Aug 25;64(35):e202507542. doi: 10.1002/anie.202507542. Epub 2025 Jul 16.
Dicarbonyl compounds are structural motifs that have been extensively utilized in synthetic chemistry, and their downstream transformations have proven valuable in synthesizing numerous heterocycles. Conventional methods for accessing such compounds include the Stetter reaction, the Michael reaction, and Friedel-Crafts acylation. However, a flexible and enabling platform for obtaining all types of 1,n-dicarbonyls remains undeveloped. Reported herein is a unified approach to access a variety of 1,n-dicarbonyls through a radical-promoted deconstructive process utilizing dual photocatalysis/carbene catalysis. The utility of this strategy is demonstrated with a broad scope with robust functional group tolerance along with application in the preparation of γ-amino esters, three-component manifolds, and the first enantioselective deconstructive synthesis of 1,5-dicarbonyls using a chiral NHC catalyst.
二羰基化合物是在合成化学中被广泛应用的结构单元，并且它们的下游转化在合成众多杂环化合物方面已被证明具有重要价值。获取此类化合物的传统方法包括施陶丁格反应、迈克尔反应和傅克酰基化反应。然而，一个用于获得所有类型的1,n -二羰基化合物的灵活且有效的平台仍未得到开发。本文报道了一种统一的方法，通过利用双光催化/卡宾催化的自由基促进解构过程来获得各种1,n -二羰基化合物。该策略的实用性在广泛的范围内得到了证明，具有强大的官能团耐受性，并且应用于γ-氨基酯的制备、三组分体系以及使用手性NHC催化剂对1,5 -二羰基化合物进行的首次对映选择性解构合成。
