Light-induced intramolecular cyclization through insertion of N-tosylhydrazone into C(sp3)-H and C=C bonds

doi:10.6023/cjoc202601024

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光促进N-对甲苯磺酰腙的分子内C(sp³)-H/C=C插入环化反应研究

李金瑞^a, 卫可悦^a, 王花^a,b,*

^a第四军医大学（空军军医大学）药学系化学制药学教研室陕西西安 710032;
^b第四军医大学（空军军医大学）军事医疗创新中心陕西西安 710032

收稿日期:2026-01-19 修回日期:2026-03-18
基金资助:
国家自然科学基金（No. 22201303）、陕西省三秦英才引进计划-青年项目基金资助项目.

Light-induced intramolecular cyclization through insertion of N-tosylhydrazone into C(sp³)-H and C=C bonds

Li Jin-Rui^a, Wei Ke-Yue^a, Wang Hua^a,b,*

^aDepartment of Chemistry, School of Pharmacy, The Fourth Military Medical University (Air Force Medical University), Xi'an Shaaxi 710032;
^bMilitary Medical Innovation Center, The Fourth Military Medical University (Air Force Medical University), Xi'an, Shaaxi 710032

Received:2026-01-19 Revised:2026-03-18
Contact: *E-mail: wanghua87@fmmu.edu.cn
Supported by:
National Natural Science Foundation of China (No. 22201303), Sanqin Talents Introduction Program of Shaanxi Province - Youth Project.

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Abstract

We report herein a light-promoted, transition-metal-free intramolecular C(sp³)-H/C=C insertion cyclization of N-tosylhydrazones has been developed. Using cesium carbonate as the base, the reaction proceeds under mild conditions via photoexcited hydrazone anions to generate highly reactive alkyl diazo intermediates. This enables highly selective insertion into both intramolecular C(sp³)-H bonds and C=C double bonds, efficiently constructing over 20 differently substituted [4.1.0]-fused bicyclic and benzofuran frameworks with yields up to 85%. The strategy exhibits broad functional group tolerance and scalability to gram-scale. Mechanistic studies indicate that the formation of photoexcited hydrazone anions is the key step in the reaction pathway.

Key words: N-tosylhydrazone, photoexcited anions, carbene insertion into C(sp³)-H bonds, carbene insertion into C=C bonds, intramolecular cyclization

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Li Jin-Rui, Wei Ke-Yue, Wang Hua. Light-induced intramolecular cyclization through insertion of N-tosylhydrazone into C(sp³)-H and C=C bonds[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202601024.

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光促进N-对甲苯磺酰腙的分子内C(sp³)-H/C=C插入环化反应研究

Light-induced intramolecular cyclization through insertion of N-tosylhydrazone into C(sp³)-H and C=C bonds

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光促进N-对甲苯磺酰腙的分子内C(sp3)-H/C=C插入环化反应研究