Recent Progress in Radical Involved Alkene Dialkylation

doi:10.6023/cjoc202312020

Abstract

Difunctionalization of alkenes constitutes a critical route for alkene derivatization and construction of molecular complexities. Yet dialkylation of alkenes allows the continuous construction of two new C(sp³)—C(sp³) bonds which is one of the most effective ways for functional alkane synthesis. Because of the high reactivity of alkyl reagents, problems such as poor regioselectivity and side reactions always appear in alkene alkylation process. In recent ten years, with the further development in radical mediated reactions, significant progress has been seen in difunctionalization of alkenes through radical path. However, challenges still exist in the implement of high selectively dialkylation of alkenes. This review aims to give a comprehensive overview about the radical involved alkene dialkylated reaction. The regioselectivity control of this reaction is elaborated from three different reaction modes: intramolecular cyclization-intermolecular alkylation, alkyl radical addition-1,2-migrated alkylation of alkenyl boron ate complexes and three-components reaction of alkenes with disparate alkylated reagents.

Key words: alkene diakylation, regioselectivity, alkyl radical, transition-metal catalysis, photocatalysis

Cite this article

Lingyi Lu, Xiaodong Qiu. Recent Progress in Radical Involved Alkene Dialkylation[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1701-1718.

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Fig. & Tab. 32

Scheme 1. General strategies for regioselective dialkylation of alkenes

Scheme 2. Intramolecular cyclization-alkylation reaction of alkene containing alkyl iodides and alkyl zinc bromides

Scheme 3. Intramolecular cyclization-alkylation reaction of alkene containing alkyl iodides and alkyl magnesium reagents

Scheme 4. Intramolecular cyclization-alkylation reaction of alkene containing alkyl bromides with alkyl bromides

Scheme 5. Intramolecular cyclization-alkylation reaction of alkene containing alkyl redox-active esters with alkyl zinc regents

Scheme 6. Intramolecular dialkylation and cyclization of alkenes

Scheme 7. Et3B initiated dialkylation of alkenyl boron ate complexes

Scheme 8. Reaction mechanism of alkene dialkylation via continues radical addition and 1,2-migration of boron ates

Scheme 9. Et3B and DTBHN initiated dialkylation of alkenyl boron ate complexes

Scheme 10. Photo initiated dialkylation of alkenyl boron ate complexes

Scheme 11. Mechanism of photo initiated dialkylation of alke- nyl boron ate complexes

Scheme 12. Photo initiated dialkylation of alkenyl boron ate complexes with the construction of ring-contracted products

Scheme 13. Photocatalyzed dialkylation of alkenyl boron ate complexes with the synthesis of ortho-diboron products

Scheme 14. Cobalt-catalyzed regioselective dialkylation of 1,3- conjugated dienes and reaction mechanism analysis

Scheme 15. Titanium-catalyzed regioselective dialkylation of styrene derivatives and reaction mechanism analysis

Scheme 16. Nickel-catalyzed regioselective dialkylation of vinyl boronates

Scheme 17. Nickel-catalyzed regioselective dialkylation of terminal alkenes with alkyl bromides

Scheme 18. Copper-catalyzed regioselective dialkylation of terminal alkenes

Scheme 19. Copper-catalyzed regioselective dialkylation of arylethylenes

Scheme 20. Nickel-catalyzed regioselective dialkylation of allyl amides

Scheme 21. Nickel-catalyzed regioselective dialkylation of aryl alkenes

Scheme 22. Nickel-catalyzed direction group assisted regioselective dialkylation of unsaturated amides

Scheme 23. Nickel-catalyzed direction group assisted regioselective dialkylation of unsaturated amides with two alkyl electrophiles

Scheme 24. Nickel-catalyzed direction group assisted regioselective dialkylation of N-vinyl amides

Scheme 25. Nickel-catalyzed direction group assisted regioselective dialkylation of styrene derivatives with high efficiency

Scheme 26. Iron-photo co-catalyzed regioselective dialkylation of alkenes

Scheme 27. Nickel-photo co-catalyzed regioselective dialkylation of aryl alkenes

Scheme 28. Nickel-photo co-catalyzed regioselective dialkylation of electron-deficient alkenes

Scheme 29. Photocatalyzed regioselective dialkylation of aryl alkenes with aldehydes and sodium trifluoromethanesulfinate

Scheme 30. Photocatalyzed regioselective dialkylation of aryl alkenes with aldehydes and aliphatic acids

Scheme 31. Photocatalyzed regioselective dialkylation of alkenes with aldehydes and alkyl oxalate monoesters

Scheme 32. Photocatalyzed regioselective dialkylation of mono-alkenes and conjugated-alkenes

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