Asymmetric Catalytic Synthesis of α,β-Unsaturated γ-Lactone and γ-Lactam

doi:10.6023/cjoc202502011

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2637-2659.DOI: 10.6023/cjoc202502011 Previous Articles Next Articles

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α,β-不饱和γ-内酯(酰胺)的不对称催化合成

沈健^a^,^b^,^†, 王彦博^b^,^†, 吴正兴^b^,^*(), 徐德锋^a^,^*(), 张万斌^b

^a 常州大学石油化工学院药学院江苏常州 213164
^b 上海交通大学化学化工学院上海市手性药物分子工程重点实验室上海 200240

收稿日期:2025-02-14 修回日期:2025-03-23 发布日期:2025-04-16
作者简介:
†共同第一作者.
基金资助:
国家自然科学基金(22471162); 郑州上海交大产业技术研究院(ZZHC-2024-001); 江苏省常州市社会发展重点研究计划(CE20205058)

Asymmetric Catalytic Synthesis of α,β-Unsaturated γ-Lactone and γ-Lactam

Jian Shen^a^,^b, Yanbo Wang^b, Zhengxing Wu^b^,^*(), Defeng Xu^a^,^*(), Wanbin Zhang^b

^a School of Petrochemical Engineering, School of Pharmacy, Changzhou University, Changzhou, Jiangsu 213164
^b Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Received:2025-02-14 Revised:2025-03-23 Published:2025-04-16
Contact: *E-mail:markxu@cczu.edu.cn;wzxtheway@sjtu.edu.cn
About author:
†The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22471162); Zhengzhou Industrial Technology Research Institute of Shanghai Jiao Tong University(ZZHC-2024-001); Key Research Plan for Social Development in Changzhou, Jiangsu Province(CE20205058)

Optically active α,β-unsaturated γ-lactone and γ-lactam serve as core scaffolds in numerous natural products. These natural products exhibit a broad spectrum of bioactivities, making them highly significant for the development of novel drugs. Furthermore, as an important class of chiral building blocks, optically active α,β-unsaturated γ-lactone and γ-lactam play a pivotal role in synthesizing diverse bioactive compounds and complex molecules. Given their versatile biological activities and potential for structural diversification, the construction of such frameworks via asymmetric catalytic synthesis has received much attention from the academic community. This review summarizes the recent advances in asymmetric catalytic methods for synthesizing α,β-unsaturated γ-lactone and γ-lactam employing transition metal catalyst, Lewis acid catalyst and organo- catalyst, and discusses the stereocontrol mechanism in representative examples and the related application value.

Key words: α,β-unsaturated γ-lactone, α,β-unsaturated γ-lactam, asymmetric catalysis

Cite this article

Jian Shen, Yanbo Wang, Zhengxing Wu, Defeng Xu, Wanbin Zhang. Asymmetric Catalytic Synthesis of α,β-Unsaturated γ-Lactone and γ-Lactam[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2637-2659.

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Fig. & Tab. 33

Scheme 1. Natural products with α,β-unsaturated γ-lactone and γ-lactam skeletons

Scheme 2. Chemical transformation and modification of α,β-unsaturated γ-lactone and γ-lactam

Scheme 3. Asymmetric catalytic synthesis of α,β-unsaturated γ-lactone and γ-lactam

Scheme 4. Asymmetric Aldol reaction of TMSOF catalyzed by chiral titanium-BINOL complex

Scheme 5. Copper(II)-catalyzed Mukaiyama Aldol reaction of TMSOF and methyl pyruvate 4

Scheme 6. Asymmetric Mukaiyama Aldol reaction

Scheme 7. Chiral quaternary ammonium salt catalyzed asymmetric Vinylogous Aldol reaction

Scheme 8. Titanium-catalyzed asymmetric Vinylogous Mannich reaction of triisopropylsilyloxyfuran with aldimines

Scheme 9. Ag-catalyzed asymmetric Vinylogous Mannich reaction of silyloxyfurans

Scheme 10. Silver(I)-catalyzed asymmetric Vinylogous Mukaiyama Mannich reaction of aldimines

Scheme 11. Copper-catalyzed asymmetric Mannich reaction of γ-butenolides and N-thiophosphinoyl ketimines

Scheme 12. Chiral spirophosphoric acid catalyzed asymmetric Vinylogous Mannich reaction

Scheme 13. Chiral Lewis acid catalyzed asymmetric Michael addition reaction

Scheme 14. Asymmetric Vinylogous Michael addition reactions catalyzed by chiral bifunctional squareamide catalysts

Scheme 15. Asymmetric vinylogous Michael addition reaction catalyzed by Al-Li-BINOL (ALB)

Scheme 16. Asymmetric allyl substitution of γ-acyloxybutenolide with phenolic nucleophiles catalyzed by palladium

Scheme 17. Pd-catalyzed asymmetric allylic alkylation (AAA) of siloxyfurans

Scheme 18. Selenium-catalyzed enantioselective oxidative cyclization of β,γ-unsaturated carboxylic acids

Scheme 19. Enantioselective synthesis of butenolides via hetero-allylic alkylation and ring closing metathesis

Scheme 20. Cascade co-catalysis reaction of chiral amines with Lewis acids

Scheme 21. Au/bifunctional phosphine ligand catalyzed asymmetric construction of α,γ-disubstituted α,β-butenolide

Scheme 22. Chiral quinine alkaloid-catalyzed asymmetric olefin isomerization

Scheme 23. Chiral bifunctional phosphine ligand enabled cooperative Cu catalysis

Scheme 24. Asymmetric Vinylogous Mukaiyama Aldol reaction of siloxy pyrrole with arylaldehydes

Scheme 25. Asymmetric Vinylogous Mannich reaction of α,β-unsaturated γ-lactam

Scheme 26. Asymmetric Vinylogous Michael addition catalyzed by dinuclear nickel catalyst

Scheme 27. Vinylogous Michael addition of α,β-unsaturated γ-lactam to α,β-unsaturated aldehydes

Scheme 28. Asymmetric Vinylogous Michael addition reaction with chiral thiourea-tertiary amine catalyst

Scheme 29. Organocatalyzed asymmetric Vinylogous Michael addition of α,β-unsaturated γ-lactam

Scheme 30. Doubly Vinylogous Michael addition between 58 and 68

Scheme 31. Nickel(II)-catalyzed asymmetric Vinylogous Michael addition

Scheme 32. Cu-catalyzed asymmetric kinetic boron conjugate addition reaction

Scheme 33. [4＋1] cyclization catalyzed by CpxRhIII (C16)

References 36

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α,β-不饱和γ-内酯(酰胺)的不对称催化合成

Asymmetric Catalytic Synthesis of α,β-Unsaturated γ-Lactone and γ-Lactam

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