常州大学王佳胤团队报道了光诱导氮中心自由基触发的，三取代烯烃的C-C键断裂/肟酯的功能化立体定向组装。相关研究成果发表在2024年2月29日出版的《中国化学》。

研究人员建立了MBH醋酸盐的通用和方便的光氧化还原催化酰化和烷基氰化方法，使得能够通过以氮为中心的自由基策略组装C(sp2)–C(sp3)键，以中等到优异的化学产率合成三取代烯烃（总共48个实例）。MBH醋酸酯与酰基（茚酮）肟酯反应得到含有1,4-二羰基的三取代烯烃。

有趣的是，在催化体系中使用曙红Y作为光催化剂，通过环酮肟酯的解构官能化形成了末端氰基锚定的三取代烯烃。值得注意的是，这些得到的1，4-二羰基化合物可以应用于后期转化，为合成二氢哒嗪-3（2H）-酮提供了重要的方法。

附：英文原文

Title: Stereospecific Assembly of Trisubstituted Alkenes via Photoinduced Nitrogen-Centered Radical-Triggered C—C Bond Cleavage/Functionalization of Oxime Esters

Author: Yu Bao, Zhi-Jie Song, Jin-Long Dai, Shenghu Yan, Yue Zhang, Jia-Yin Wang, Guigen Li

Issue&Volume: 2024-02-29

Abstract: A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established, enabling the assembly of the C(sp2)–C(sp3) bond by a nitrogen-centered radical strategy for the synthesis of trisubstituted alkenes in moderate to excellent chemical yields (48 examples in total). The reaction of MBH acetates with acyl (indanone) oxime esters afforded trisubstituted alkenes containing 1,4-dicarbonyl groups. Interestingly, the use of Eosin Y as a photocatalyst in the catalytic system resulted in the formation of distal cyano group-anchored trisubstituted alkenes via deconstructive functionalization of cycloketone oxime esters. Notably, these resulting 1,4-dicarbonyl compounds could be applied to late-stage transformations, providing important methods for the synthesis of dihydropyridazin-3(2H)-one.

DOI: 10.1002/cjoc.202300774

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202300774