Transition Metal-Catalyzed Asymmetric Migratory Allylic C—H Functionalization of Remote Dienes

doi:10.6023/cjoc202406047

Abstract

Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.

Key words: remote dienes, metal walking, migratory allylic substitution, allylic C—H bond functionalization, asymmetric synthesis

Cite this article

Jingming Zhang, Zhitao He. Transition Metal-Catalyzed Asymmetric Migratory Allylic C—H Functionalization of Remote Dienes[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 592-601.

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Fig. & Tab. 17

Scheme 1. Transition metal-catalyzed allylic C—H activation

Scheme 2. Pd-catalyzed hydrofunctionalization of unsaturated bonds

Scheme 3. Pd-catalyzed asymmetric hydroalkylation of skipped dienes

Scheme 4. The proposed mechanism for Pd-catalyzed remote hydroalkylation

Scheme 5. Migratory hydrofluoroalkylation of remote dienes

Scheme 6. Nucleophilic functionalization of remote dienes via migratory 1,5-addition

Scheme 7. Asymmetric hydroalkylation of remote dienes and its applications

Scheme 8. Proposed mechanism for directed migratory allylic substitution

Scheme 9. Pd-catalyzed stereoselective hydroamination of remote dienes

Scheme 10. General design for Pd-catalyzed difunctionalization of remote dienes

Scheme 11. Early studies on Pd-catalyzed nonasymmetric difun- ctionalization of remote dienes

Scheme 12. Zhou’s work on asymmetric Heck arylation/amina- tion of nonconjugated dienes

Scheme 13. Zhou’s work on asymmetric Heck arylation/alkyla- tion of 1,4-cyclohexadienes

Scheme 14. Pd-catalyzed intramolecular difunctionalization of remote dienes

Scheme 15. Pd-catalyzed tandem oxidative migratory difunctionalization of nonconjugated dienes

Scheme 16. Ni-catalyzed enantioselective migratory hydrocyanation to construct allyl nitriles

Scheme 17. Ni-catalyzed stereoselective migratory hydroalkylation of non-conjugated dienes

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