烯烃和炔烃的氘官能团化反应研究进展

doi:10.6023/cjoc202602008

摘要/Abstract

氘代化合物广泛应用于材料科学、有机合成研究和药物化学等领域. 特别是在制药行业, 向药物分子的特定位置引入氘原子在改善药物的药代动力学(PK)特性及调节药物代谢等方面具有显著优势. 不饱和键(烯烃和炔烃)的氘官能团化反应是合成氘代化合物的一种重要手段, 为精准合成氘代分子提供了直接、高效、便捷的途径. 近年来, 该策略日益受到人们重视, 并已衍生出一系列可实现不饱和键(烯烃和炔烃)选择性氘官能团化的方法. 对近些年烯烃及炔烃氘官能团化反应的发展进行了总结, 内容涵盖了多种催化体系, 包括光催化、电催化及过渡金属催化等.

关键词: 氘代化合物, 氘官能团化, 不饱和键, 烯烃和炔烃

Deuterium-labeled compounds are widely employed in various fields such as materials science, organic synthesis, and medicinal chemistry. Particularly in the pharmaceutical industry, the site-specific introduction of deuterium atoms into drug molecules offers significant advantages in improving pharmacokinetic (PK) properties and modulating drug metabolism. The deuterofunctionalization of unsaturated bonds (e.g., alkenes and alkynes) serves as a crucial strategy for the synthesis of deuterated compounds, providing a direct, efficient, and convenient route for the precise construction of deuterated molecules. In recent years, this approach has gained increasing attention and has led to the development of a series of methods capable of achieving selective deuterofunctionalization of unsaturated bonds (alkenes and alkynes). The recent advances in deuterofunctionalization reactions of alkenes and alkynes are summarized, covering diverse catalytic systems including photocatalysis, electrocatalysis, transition-metal catalysis.

Key words: deuterium-labeled compound, deuterofunctionalization, unsaturated bond, alkene and alkyne

引用此文

付明月, 董战, 陈伟, 陈铁根. 烯烃和炔烃的氘官能团化反应研究进展[J]. 有机化学, 2026, 46(6): 2207-2226.

Mingyue Fu, Zhan Dong, Wei Chen, Tie-Gen Chen. Recent Advances in Deuterium Functionalization Reactions of Alkenes and Alkynes[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2207-2226.

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图/表 30

图1. 氢和氘的差异

Figure 1. Differences between hydrogen and deuterium

图2. 氘代药物分子

Figure 2. Deuterated drug molecules

图式1. 有机光催化合成对映体富集的α-氘代氨基酸

Scheme 1. Organophotocatalytic synthesis of enantioenriched α-deuterated amino acids

图式2. 光氧化还原催化α-氨基酸衍生物的氘烷/芳基化

Scheme 2. Photoredox catalyzed deuteroalkylation and deuteroarylation of α-amino acid derivatives

图式3. 烯烃氘酰化反应

Scheme 3. Deuteroacylation of alkenes

图式4. 电还原烯烃氘官能团化

Scheme 4. Electroreductive deuterofunctionalization of alkenes

图式5. 1,3-烯炔的电化学1,4-氘代烷基化

Scheme 5. Electrochemical 1,4-deuteroalkylation of 1,3-enynes

图式6. 有机介质介导的烯烃电还原氘芳基化

Scheme 6. Organo-mediated electroreductive deuteroarylation of alkenes

图式7. 电催化炔烃氘芳基化

Scheme 7. Electrocatalytic deuterium-arylation of alkynes

图式8. 电催化炔烃的氘代羧化反应

Scheme 8. Electrocatalytic deuterocarboxylation of alkynes

图式9. 1,3-烯炔的电还原1,4-氘芳基化

Scheme 9. Electroreductive 1,4-deuteroarylation of 1,3-enynes

图式10. 1,1-二烷基取代烯烃的不对称氘烷基化

Scheme 10. Asymmetric deuterioalkylation of 1,1-disubstituted alkenes

图式11. 氘标记实验

Scheme 11. Deuterium labeling experiment

图式12. 钴催化烯烃氘烷基化

Scheme 12. Cobalt-catalyzed deuterium-alkylation of alkenes

图式13. 镍催化炔烃合成氘代烯丙胺

Scheme 13. Nickel-catalyzed synthesis of deuterated allylic amines from alkynes

图式14. 氘标记实验

Scheme 14. Deuterium labeling experiment

图式15. Katritzky盐介导的烯烃氘烷基化

Scheme 15. Deuteroalkylation of alkenes enabled by Katritzky salts

图式16. 铁催化炔烃氘烷基化反应

Scheme 16. Iron-catalyzed deuteroalkylation of alkynes

图式17. 氘标记实验

Scheme 17. Deuterium labeling experiment

图式18. 苯环专一性活化实现选择性氘代二氟烷基化

Scheme 18. Benzene-specific activation for selective deutero-difluoroalkylation

图式19. 钌催化实现1,3-烯炔的C—H插入

Scheme 19. Ruthenium-catalyzed C—H insertion of 1,3-enynes

图式20. 光催化烯烃氘胺化反应

Scheme 20. Photocatalyzed deuteroamination of alkenes

图式21. 铁催化烯烃氘氯化反应

Scheme 21. Iron-catalyzed deuteriochlorination of alkenes

图式22. 铁催化1,6-烯炔的氘代氯化反应

Scheme 22. Iron-catalyzed deuterochlorination of 1,6-enynes

图式23. 铁催化1,n-烯炔的氘代溴化反应

Scheme 23. Iron-catalyzed deuterobromination of 1,n-enynes

图式24. 光催化烯烃氘硅化反应

Scheme 24. Photocatalytic deuteriosilylation of alkenes

图式25. 光催化环外烯烃的氘官能团化反应

Scheme 25. Photocatalytic deuterofunctionalization of exocyclic alkenes

图式26. 电化学合成氘代乙烯基硫醚

Scheme 26. Electrosynthesis of deuterated vinyl sulfides

图式27. 非活化烯烃的氘代甲硫基化反应

Scheme 27. Deuteriomethylthiolation of unactivated alkenes

图式28. 铜催化炔烃的氘-氧官能团化反应

Scheme 28. Copper-catalyzed synthesis of deuterated enol esters

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