烯基自由基参与的分子内氢原子转移反应的新进展

doi:10.6023/cjoc202108027

摘要/Abstract

近年来烯基自由基引发的氢原子转移反应受到了广泛的关注. 利用该策略可以实现自由基成环反应和区域选择性的远程sp³碳氢键官能化反应, 包括碳氢键烯基化、炔基化、卤化及芳基化等反应. 在该类反应中, 烯基自由基的产生方式由传统的烯基卤化物单电子还原, 拓展到通过外加自由基对炔基的加成. 这些反应依据底物类型的不同, 机理路径也有所不同. 通常情况下, 攫氢产生的烷基自由基会重新加成到烯烃上, 实现成环反应. 如果以炔丙醇作为底物, 成环后形成的烷基自由基易发生开环反应实现烯烃迁移. 当以非末端炔烃为底物时, 可能发生分子间的自由基官能化反应. 烯基自由基参与氢原子转移反应具有区域选择性佳、原子经济性好以及反应模式多样等优点. 对该研究领域的近期进展进行了综述.

关键词: 自由基反应, 碳氢键活化, 氢迁移, 官能团迁移, 烯基自由基

In recent years, vinyl radical-mediated hydrogen atom transfer (HAT) has received increasing attention. This protocol provides an efficient pathway for radical cyclization and regioselective C(sp³)—H bond functionalization including vinylation, alkynylation, halogenation, arylation, etc. Generally, vinyl radicals are generated from single electron reduction of vinyl halides or the addition of extra radical to alkynes. The reaction pathways depend on substrates. For example, the resulting alkyl radical arising from vinyl radical-mediated HAT process is prone to be intramolecularly re-added to alkene, leading to cyclic products. When employing specific propargyl alcohols as substrates, the cyclic alkyl radical intermediate undergoes β-scission of C—C bond to realize vinyl migration. In addition, intermolecular radical trapping usually occurs by using internal alkynes. The transformation based on vinyl radical-mediated HAT features high regioselectivity, good atom-economy, and broad diversity of reaction modes. The recent advances in this research area are summarized.

Key words: radical reaction, C—H bond functionalization, 1,5-hydrogen atom transfer, functional group migration, vinyl radical

引用此文

乐柏佟, 吴新鑫, 朱晨. 烯基自由基参与的分子内氢原子转移反应的新进展[J]. 有机化学, 2022, 42(2): 458-470.

Baitong Yue, Xinxin Wu, Chen Zhu. Recent Advances in Vinyl Radical-Mediated Hydrogen Atom Transfer[J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 458-470.

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图/表 21

图式1. 通过烯基自由基参与的氢转移策略实现三类转化

Scheme 1. Three types of transformations involving vinyl radical-mediated HAT

图式2. 烯基自由基诱导的炔烃氢磺酰化反应

Scheme 2. Vinyl radical-induced hydrosulfonylation of alkyne

图式3. 烯基自由基参与的多步串联环化反应

Scheme 3. Vinyl radical-mediated cascade reaction for constructing fused ring

图式4. 烯基自由基参与的6(5)-6-5稠环构建

Scheme 4. Vinyl radical-mediated construction of 6(5)-6-5 fused ring

图式5. 烯基自由基参与的串联反应构建稠环

Scheme 5. Vinyl radical-mediated cascade reaction for constructing fused ring

图式6. 脂肪酸脱羧引发烯基自由基的串联环化

Scheme 6. Vinyl radical-mediated cascade cyclization triggered by decarboxylation of aliphatic acids

图式7. 烯基自由基参与构建的[6.5.6]稠环反应

Scheme 7. Vinyl radical-mediated cascade reaction for constructing [6.5.6] fused ring

图式8. 烯基自由基参与的环状砜化合物的构建

Scheme 8. Vinyl radical-mediated cascade reaction for constructing cyclic sulfones

图式9. 烯基自由基参与的[4+2]环化反应

Scheme 9. Vinyl radical-mediated [4+2] cyclization

图式10. 烯基自由基参与的炔烃三官能化反应

Scheme 10. Vinyl radical-mediated tri-functionalization of alkynes

图式11. 烯基自由基参与的远端sp3碳氢键的区域选择性烯基化

Scheme 11. Vinyl radical-mediated regioselective vinylation of remote C(sp3)—H bonds

图式12. 烯基自由基参与的sp3碳氢键的区域选择性乙烯基三氟甲基硫醚化

Scheme 12. Vinyl radical-mediated regioselective trifluoromethylthiolation of C(sp3)—H bond

图式13. 烯基自由基参与的sp3碳-氢键的区域选择性磺酰烯基化

Scheme 13. Regioselective sulfonylvinylation of the unactivated C(sp3)—H bond mediated by vinyl radical

图式14. 环酮肟酯开环促进的sp3碳-氢键磺酰烯基化

Scheme 14. Sulfonylvinylation of C(sp3)—H bond enabled by ring-opening of cycloketone oxime

图式15. 烷烃参与的sp3碳-氢键烯基化

Scheme 15. Vinylation of C(sp3)—H bond involving alkanes

图式16. 通过1,5-氢迁移实现光催化的远端氧氟烷基化

Scheme 16. Photocatalytic remote oxyfluoroalkylation of heteroalkynes via 1,5-HAT

图式17. 烯基自由基参与的炔基远端三氟甲基烯基化

Scheme 17. Vinyl radical-mediated remote trifluoromethyl- alkynylation of thioalkynes

图式18. 烯基自由基参与的炔基远端氟烷基卤化

Scheme 18. Vinyl radical-mediated remote fluoroalkyl-halogenation of thioalkynes

图式19. 烯基自由基参与的炔基远端氟烷基卤化

Scheme 19. Vinyl radical-mediated remote fluoroalkyl-halogenation of thioalkynes

图式20. 烯基自由基参与的sp3碳氢键芳基化

Scheme 20. Vinyl radical-mediated arylation of C(sp3)—H bond

图式21. 烯基碘化物参与的自由基环合反应

Scheme 21. Vinyl iodide-mediated radical cyclization

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