涉及未活化环烷烃C(sp3)—H官能化的自由基串联环化反应

doi:10.6023/cjoc202208001

摘要/Abstract

未活化环烷烃是最广泛的自然资源之一, 发展温和、高效的未活化环烷烃C(sp³)—H官能化策略具有重要意义, 同时, 开发环状化合物的制备方法是有机合成和药物化学的研究热点. 涉及未活化环烷烃C(sp³)—H官能化的自由基串联环化因具有反应条件温和、反应活性高等优势而能同时满足上述需求, 以高原子和高步骤经济性的方式构建具有潜在应用价值的环状分子. 从铁催化、铜催化以及无金属催化剂体系的角度出发, 简要论述了近十年涉及未活化环烷烃C(sp³)—H官能化的自由基串联环化反应研究进展.

关键词: 未活化环烷烃, C(sp³)—H官能化, 自由基串联环化, 催化体系

Unactivated cycloalkane is one of the most extensive natural resources, and it is of great significance to develop mild and efficient strategies to achieve C(sp³)—H of unactivated cycloalkanes. At the same time, the preparation of ring compounds is one of the hotspots in organic synthesis and medicinal chemistry. Because of the advantages of mild conditions and high reactivity, radical cascade cyclization involving C(sp³)—H functionalization of unactivated cycloalkanes can simultaneously meet the above requirements and synthesize cyclic molecules with potential applications in high atomic- and step- economy manner. In this review, from the point of view of iron catalysis, copper catalysis, and metal-catalyst-free systems, the advances in radical cascade cyclization involving C(sp³)—H functionalization of unactivated cycloalkanes in recent ten years are summarized.

Key words: unactivated cycloalkane, C(sp³)—H functionalization, radical cascade cyclization, catalytic system

引用此文

易荣楠, 李姣哲, 王东凯, 魏文廷. 涉及未活化环烷烃C(sp³)—H官能化的自由基串联环化反应[J]. 有机化学, 2022, 42(12): 4111-4121.

Rongnan Yi, Jiaozhe Li, Dongkai Wang, Wenting Wei. Radical Cascade Cyclization Involving C(sp³)—H Functionalization of Unactivated Cycloalkanes[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4111-4121.

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图/表 22

图式1. 1,7-烯炔与简单环烷烃的自由基串联双环化反应

Scheme 1. Radical cascade bi-cyclization of 1,7-enynes with simple cycloalkanes

图式2. 氧拴1,7-烯炔与简单环烷烃的自由基串联双环化反应

Scheme 2. Radical cascade bi-cyclization of O-tethered 1,7- enynes with simple cycloalkanes

图式3. 烯酰胺与简单环烷烃的自由基串联环化反应

Scheme 3. Radical cascade cyclization of acrylamides with simple cycloalkanes

图式4. 丙烯酰胺与简单烷烃的烷基/芳基化反应

Scheme 4. Alkylarylation of acrylamides with simple alkanes

图式5. 异氰酸酯与简单环烷烃的自由基串联环化反应

Scheme 5. Radical cascade cyclization of isocyanides with simple cycloalkanes

图式6. N-烯丙基苯胺与简单环烷烃的自由基串联环化反应

Scheme 6. Radical cascade cyclization of N-allyl anilines with simple cycloalkanes

图式7. 活化炔烃与未活化环烷烃的自由基串联环化反应

Scheme 7. Radical cascade cyclization of activated alkynes with unactivated cycloalkanes

图式8. 二芳基(芳基乙炔)磷氧化物与未活化环烷烃的自由基串联环化反应

Scheme 8. Radical cascade cyclization of diaryl(arylethynyl)- phosphine oxides with unactivated cycloalkanes

图式9. 硝基二芳基炔酮与环烷烃的烷基化/脱硝基去芳构化反应

Scheme 9. Alkylation/denitrative dearomatization of nitrobiarylalkynones with cycloalkanes

图式10. 吡啶衍生物与简单烷烃的自由基串联环化反应

Scheme 10. Radical cascade cyclization of pyridines with simple alkanes

图式11. 烯烃酰胺与简单烷烃的自由基串联环化反应

Scheme 11. Radical cascade cyclization of olefinic amides with simple alkanes

图式12. 烯基叠氮衍生物和环烷烃的自由基氧化环化反应

Scheme 12. Oxidative cyclization of vinyl azides with cycloalkanes

图式13. 芳基异氰酸酯/异硫氰酸酯和简单烷烃的自由基串联环化反应

Scheme 13. Radical cascade cyclization of aryl isocyanates/ isothiocyanates with simple alkanes

图式14. N-苯基-肉桂酰胺与简单烷烃的自由基串联环化

Scheme 14. Radical cascade cyclization of N-phenyl-cinnam- amides with simple alkanes

图式15. N-取代烯丙基苯甲酰胺与环烷烃的自由基串联环化反应

Scheme 15. Radical cascade cyclization of N-allylbenzamides with cycloalkanes

图式16. 2-氰基-3-芳基衍生的丙烯酰胺与简单环烷烃的自由基串联环化反应

Scheme 16. Radical cascade cyclization of 2-cyano-3-arylani- line derived acrylamides with simple cycloalkanes

图式17. 2-芳基苯并咪唑与未活化环烷烃的自由基串联环化反应

Scheme 17. Radical cascade cyclization of 2-arylbenzoimidazoles with unactivated cycloalkanes

图式18. 双芳基乙烯基醚与未活化烷烃的自由基串联环化反应

Scheme 18. Radical cascade cyclization of biaryl vinyl ethers with unactivated alkanes

图式19. 烯烃取代喹唑啉酮与未活化烷烃的自由基串联环化反应

Scheme 19. Radical cascade cyclization of alkene substituted quinazolinones with unactivated alkanes

图式20. 乙烯基异氰酸酯与未活化烷烃的自由基串联环化反应

Scheme 20. Radical cascade cyclization of vinyl isocyanides with unactivated alkanes

图式21. 异腈衍生物与环烷烃的自由基串联环化反应

Scheme 21. Radical cascade cyclization of isonitriles with cycloalkanes

图式22. 炔丙酮与烷烃的碳环化反应

Scheme 22. Carboannulation of ynones with alkanes

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涉及未活化环烷烃C(sp³)—H官能化的自由基串联环化反应

Radical Cascade Cyclization Involving C(sp³)—H Functionalization of Unactivated Cycloalkanes

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