Ma Chunhua, Shang Linchun, Jiang Na, Ding Qingjie, Cao Zhong-Yan, Jiang Yuqin, Yu Bing
Collaborative Innovation Centre of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Engineering Research Centre of Chiral Hydroxyl Pharmaceutical, Henan Engineering Laboratory of Chemical Pharmaceutical and Biomedical Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, China.
Org Lett. 2025 Aug 15;27(32):8863-8868. doi: 10.1021/acs.orglett.5c02358. Epub 2025 Aug 3.
Given the essential and valuable characteristics of cyclopropane scaffolds in pharmaceutical and organic chemistry, general strategies for their construction are highly desirable. However, the divergent synthesis of spirocyclopropanes and 1,1-substituted cyclopropanes using the same starting materials remains a challenge. Herein, we disclose a visible-light-promoted procedure for the concise and divergent construction of spirocyclopropyl succinimides (28 examples, yields up to 95%) and cyclopropyl-acetamides (18 examples, yields up to 82%) from -substituted oxamic acids and methyl 4-chloro-2-methylenebutanoate by radical addition/polar crossover/cyclization/cyclization (RAPCC) and radical addition/polar cyclization (RAPC) cascades. The versatility and practicality of this photocatalytic approach are underscored by its good functional group tolerance and broad substrate scope, which include tolerating the valuable handles and late-stage modification of medicinal agents.
鉴于环丙烷骨架在药物化学和有机化学中具有重要且有价值的特性，非常需要构建它们的通用策略。然而，使用相同的起始原料对螺环丙烷和1,1-取代环丙烷进行不同的合成仍然是一个挑战。在此，我们公开了一种可见光促进的方法，通过自由基加成/极性交叉/环化/环化（RAPCC）和自由基加成/极性环化（RAPC）串联反应，从α-取代的草氨酸和4-氯-2-亚甲基丁酸甲酯简洁且不同地构建螺环丙基琥珀酰亚胺（28个例子，产率高达95%）和环丙基乙酰胺（18个例子，产率高达82%）。这种光催化方法的多功能性和实用性通过其良好的官能团耐受性和广泛的底物范围得到强调，其中包括耐受药物的重要官能团和后期修饰。
