Application of Functional Group Migration Strategies in Photodriven Difunctionalization of Unsaturated Hydrocarbons

doi:10.6023/cjoc202408025

Abstract

Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds. It allows for the introduction of two functional groups into the unsaturated bond in a single step, facilitating the efficient construction of complex molecular architectures, which has been widely utilized in material chemistry, pharmaceutical and fine chemical synthesis. Recently, significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis. However, highly selective difunc- tionalization reactions still remain challenging. The research progress of selective difunctionalization of unsaturated hydro- carbons using a free radical addition/functional group migration strategy over the past decade is summarized, and synthetic strategies and key reaction steps are systematically elaborated.

Key words: visible-light-driven, unsaturated hydrocarbon, functional group migration, difunctionalization

Cite this article

Chonglong He, Youkang Zhou, Xinhua Duan, Le Liu. Application of Functional Group Migration Strategies in Photodriven Difunctionalization of Unsaturated Hydrocarbons[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1478-1508.

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Fig. & Tab. 47

Scheme 1. Mechanistic overview for radical difunctionalization of unsaturated hydrocarbon via functional group migration

Scheme 2. Radical difunctionalization of alkenes

Scheme 3. Aryl migration mediated difunctionalization of tertiary alcohol-substituted alkenes

Scheme 4. 1,3- or 1,4-aryl migration of distal olefinic tertiary alcohols

Scheme 5. Fluoroalkyl heteroarylation of distal olefinic tertiary alcohol

Scheme 6. Photoredox mediated remote heteroaryl migration and radical polar crossover deuteration

Scheme 7. Difunctionalization of alkenes bearing distal N-sulfonyl acrylamide skeleton

Scheme 8. Asymmetric difunctionalization of N-sulfinyl acrylamide

Scheme 9. Photocatalyzed cascade reaction of ene-ynamides

Scheme 10. Intramolecular difunctionalization of unactivated alkene based sulfonamide skeleton

Scheme 11. Photocatalized alkyne difunctionaliztion of N-(arylsulfonyl)propiolamide

Scheme 12. Difunctionalization of alkynes bearing N-sulfonyl amide skeleton

Scheme 13. Acyl arylation of alkynes based on sulfonyl amide skeleton

Scheme 14. Site-selective trifluoromethylative pyridylation of unactivated alkenes

Scheme 15. Photoinduced [3＋2] cycloaddition of alkenes

Scheme 16. Aryl migration from boron center for the difunctionalization of alkenes

Scheme 17. Aryl migration from olefins bearing adjacent all-carbon quaternary center

Scheme 18. Difunctionalization on distal olefinic sulfone framework

Scheme 19. Difunctionalization of alkenes based on distal aryl sulfonate framework

Scheme 20. Difunctionalization of alkynes on aryl alkynoate skeleton

Scheme 21. Phenyl disulfide initiated difunctionalization of alkynes

Scheme 22. Difunctionalization of α-allenols via aryl migration

Scheme 23. Bifunctional reagent mediated difunctionalization of unsaturated hydrocarbons

Scheme 24. Sufonyl alkyl halide as bifunctional reagent for the difunctionalization of alkenes

Scheme 25. Sufonyl alkyl halide as bifunctional reagent for the difunctionalization of alkynes

Scheme 26. Aryl sulfonamide-based bifunctional reagents for the difunctionalization of alkenes

Scheme 27. N-sulfinylamine-based bifunctional reagents for the difunctionalization of alkenes

Scheme 28. Chiral aryl sulfinyl amide as bifunctional reagents for the asymmetric alkene difunctionalization

Scheme 29. Aryl sulfonylacetate as bifunctional reagents for the difunctionalization of alkynes

Scheme 30. Aryl sulfonylacetate as bifunctional reagents for the difunctionalization of alkenes

Scheme 31. Aryl diazonium salt as bifunctional reagent for alkene difunctionalization

Scheme 32. Cyano group migration in alkene difunctionaliztion

Scheme 33. Cyanofluoroalkylation of unactivated alkene via cyano migration

Scheme 34. Trifunctionaliztion of hexeneitrile involving cyano migration

Scheme 35. Sulfonylcyanation of alkenes via cyano migration

Scheme 36. Cyclopropanation via cyano migration/radical-polar crossover

Scheme 37. Fluoroalkylcyanation of alkenes via cyano migration

Scheme 38. Trifluoromethylcyanation of alkenes via cyano migration

Scheme 39. Di-π-methane rearrangement of distal di-cyano alkenes

Scheme 40. Difunctionalization of alkenes via alkynyl or alkenyl migration

Scheme 41. Difunctional of alkenes via unsaturated hydrocarbon migration

Scheme 42. Aldehyde and oxime migration during the difunctionalization

Scheme 43. Alkyloximation of alkenes reaction

Scheme 44. Difunctionalization of unactivated alkenes via ligand-to-metal charge transfer (LMCT) induced acyl or aryl migration

Scheme 45. Difunctionalization of alkenes via Bpin migration

Scheme 46. Difunctionalization of alkenes via phosphinyl migration

Scheme 47. Difunctionalization via imine migration reaction

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