Recent Advances in Deuterium Functionalization Reactions of Alkenes and Alkynes

doi:10.6023/cjoc202602008

Abstract

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

Cite this article

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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Fig. & Tab. 30

Figure 1. Differences between hydrogen and deuterium

Figure 2. Deuterated drug molecules

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

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

Scheme 3. Deuteroacylation of alkenes

Scheme 4. Electroreductive deuterofunctionalization of alkenes

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

Scheme 6. Organo-mediated electroreductive deuteroarylation of alkenes

Scheme 7. Electrocatalytic deuterium-arylation of alkynes

Scheme 8. Electrocatalytic deuterocarboxylation of alkynes

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

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

Scheme 11. Deuterium labeling experiment

Scheme 12. Cobalt-catalyzed deuterium-alkylation of alkenes

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

Scheme 14. Deuterium labeling experiment

Scheme 15. Deuteroalkylation of alkenes enabled by Katritzky salts

Scheme 16. Iron-catalyzed deuteroalkylation of alkynes

Scheme 17. Deuterium labeling experiment

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

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

Scheme 20. Photocatalyzed deuteroamination of alkenes

Scheme 21. Iron-catalyzed deuteriochlorination of alkenes

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

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

Scheme 24. Photocatalytic deuteriosilylation of alkenes

Scheme 25. Photocatalytic deuterofunctionalization of exocyclic alkenes

Scheme 26. Electrosynthesis of deuterated vinyl sulfides

Scheme 27. Deuteriomethylthiolation of unactivated alkenes

Scheme 28. Copper-catalyzed synthesis of deuterated enol esters

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