烯烃立体选择性卤胺化的研究进展

doi:10.6023/cjoc202505019

摘要/Abstract

烯烃与胺基和卤素基的区域选择性和立体选择性相邻双官能化可以通过催化卤化方法有效地完成. 立体选择性卤胺化反应已成为将卤素官能团引入手性胺的重要方法, 在药物化学和有机合成中得到了广泛应用. 过去几十年来, 在催化系统和方法创新的推动下, 这一领域取得了重大进展. 使用手性催化剂对官能化和非官能化烯烃进行烯烃立体选择性卤胺化已成为一个突出的研究领域. 全面概述了过去几十年来立体选择性卤胺化领域取得的重大进展; 探讨了催化剂设计方面的创新, 这些创新促进了更高效、更具选择性的转化; 还分析了反应条件的优化, 这对提高这些反应的整体性能和适用性至关重要. 此外, 对立体选择性卤胺化的未来进行了展望.

关键词: 分子间, 分子内, 立体选择性卤胺化, 催化, 烯烃

The regioselective and stereoselective vicinal difunctionalization of alkenes with amino and halogen groups can be efficiently achieved through catalytic halogenation methods. Stereoselective haloamination reactions have emerged as an important strategy for introducing halogen functionalities into chiral amines, finding widespread applications in pharmaceutical chemistry and organic synthesis. Over the past few decades, significant progress has been made in this field, driven by innovations in catalytic systems and methodologies. The stereoselective haloamination of both functionalized and non-functionalized alkenes using chiral catalysts has become a prominent area of research. This review provides a compre- hensive overview of the major advances in stereoselective haloamination achieved in recent decades. It explores innovations in catalyst design that have facilitated more efficient and selective transformations. The optimization of reaction conditions is also analyzed, as it plays a crucial role in enhancing the overall performance and applicability of these reactions. Furthermore, the review offers perspectives on the future of stereoselective haloamination.

Key words: intermolecular, intramolecular, stereoselective haloamination, catalysis, olefins

引用此文

钟国, 白萌冉, 崔斌, 孙慧. 烯烃立体选择性卤胺化的研究进展[J]. 有机化学, 2025, 45(12): 4271-4289.

Guo Zhong, Mengran Bai, Bin Cui, Hui Sun. Advances in Stereoselective Haloamination of Alkenes[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4271-4289.

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图/表 39

图式1. N-氯邻苯二甲酰亚胺作为卤胺化反应的氮源

Scheme 1. N-Chlorophthalimide as nitrogen source for haloamination reaction

图式2. 以N-氯邻苯二甲酰亚胺为氮源进行卤胺化反应的反应机理

Scheme 2. Reaction mechanism of N-chlorophthalimide as nitrogen source for haloamination reaction

图式3. MnI2高效催化非活化烯烃的区域选择性碘胺化反应

Scheme 3. Regioselective iodoamination of unactivated alkenes catalyzed efficiently by MnI2

图式4. 无催化剂可见光介导的烯烃碘胺化反应

Scheme 4. Catalyst-free visible-light-mediated iodoamination of olefins

图式5. N-氯代丁二酰亚胺光诱导氯胺化环化级联反应

Scheme 5. Photoinduced chloroamination cyclization cascade with N‑chlorosuccinimide

图式6. Cu(OTf)2催化肉桂酸酯的不对称氯胺化反应

Scheme 6. Cu(OTf)2-catalyzed asymmetric chloroamination of cinnamate

图式7. CuOTf催化肉桂酸酯氯胺化

Scheme 7. CuOTf-catalyzed cinnamon ester chloroamination

图式8. 过渡金属催化肉桂酸盐的立体选择性卤胺化反应

Scheme 8. Transition metal-catalyzed stereoselective haloamination of cinnamates

图式9. 以N-氯-N-磺胺钠为氮、氯源的立体选择性氯胺化反应

Scheme 9. Stereoselective chloroamination reaction utilizing N- chloro-N-sodium sulfonamide as the nitrogen and chlorine source

图式10. 离子液体介导的烯烃立体选择性卤胺化反应

Scheme 10. Ionic liquid-mediated stereoselective haloamination of olefins

图式11. 螯合控制的立体选择性卤胺化

Scheme 11. Chelation-controlled stereoselective haloamination

图式12. α,β-不饱和腈的卤胺化反应

Scheme 12. Haloamination of α,β-unsaturated nitrile

图式13. α,β-不饱和酮的立体选择性氯胺化反应

Scheme 13. Stereoselective chloroamination of α,β-unsaturated ketones

图式14. 铁过渡金属催化的分子间立体选择性卤胺化反应

Scheme 14. Intermolecular stereoselective haloamination catalyzed by iron transition metals

图式15. 苯乙烯的氯胺化反应

Scheme 15. Chloroamination of styrene

图式16. 钯催化的新型对映选择性氯胺化反应

Scheme 16. A novel palladium-catalyzed enantioselective chloroamination

图式17. CuI、MnSO4或V2O5催化多种烯烃的溴胺化反应

Scheme 17. Bromoamination of a variety of olefins catalyzed by CuI, MnSO4 or V2O5

图式18. 铜粉催化α,β-不饱和酮的区域和立体选择性溴胺化反应

Scheme 18. Reregional and stereoselective bromoamination rea- ctions of α,β-unsaturated ketones catalyzed by copper powder

图式19. 立体选择性溴胺化反应

Scheme 19. A stereoselective bromoamination reaction

图式20. 手性L4-Sc(NTf2)3配合物催化查尔酮的立体选择性溴胺化反应

Scheme 20. Stereoselective bromoamination reaction of chalcone catalyzed by chiral L4-Sc(NTf2)3 complex

图式21. 铜(II)催化非活性烯烃的对映选择性卤胺化反应

Scheme 21. Enantioselective haloamination of copper(II)-catalyzed unactive olefins

图式22. 查尔酮与4-芳基-4-氧丁基-2-烯酸酯为底物的不对称碘胺化反应

Scheme 22. Asymmetric iodoamination reaction of chalcone and 4-aryl-4-oxobutyl-2-enoate as substrates

图式23. Pd(II)催化烯丙醇或烯丙胺的不对称卤胺化反应

Scheme 23. Asymmetric haloamination of allyl alcohols or allyl amines catalyzed by Pd(II)

图式24. (Salen)Mn(III)催化剂实现烯烃卤胺化/手性氮吡啶中间体的对映选择性环化

Scheme 24. (Salen)Mn(III)-catalyzed enantioselective cyclization of olefin haloamination/chiral nitrogen pyridine intermediates

图式25. 氨基甲酸酯对映选择性近端碘胺化和氯胺化

Scheme 25. Enantioselective proximal iodoamination and chloroamination of olecarbamates

图式26. 有机催化对映选择性烯烃氟胺化

Scheme 26. Organocatalytic enantioselective olefin fluoroamination

图式27. 烯烃的对映选择性氟胺化

Scheme 27. Enantioselective fluorination of alkenes

图式28. 碘催化的分子间选择性氟胺化

Scheme 28. Iodine-catalyzed intermolecular selective fluoroamination

图式29. 采用高价碘(III)的GAP法进行的立体选择性氯胺化反应

Scheme 29. Stereoselective chloroamination via GAP method of high-valent iodine(III)

图式30. PhI(OAc)2在纯水中催化缺电子烯烃的溴胺化反应

Scheme 30. Bromoamination of electron-deficient olefins in pure water catalyzed by PhI(OAc)2

图式31. 氨基硫代氨基甲酸酯催化对映选择性溴胺化环化

Scheme 31. Aminothiocarbamate catalyzes enantioselective bromoamination cyclization

图式32. 烯丙醇对映选择性溴胺化反应

Scheme 32. Enantioselective bromoamination reaction of allyl alcohol

图式33. 氨基硫代氨基甲酸酯催化的不对称溴胺化反应

Scheme 33. Asymmetric bromoamination catalyzed by amino-thiocarbamate

图式34. 用C2对称环催化剂催化N-溴酰亚胺的不对称溴胺化反应

Scheme 34. Asymmetric bromoamination of N-bromophtha- limide catalyzed by a C2-symmetric cyclic catalyst for cyclization of N-bromophthalimide

图式35. BINAP(S)利用NBS催化烯丙基苯胺的对映选择性溴胺化反应

Scheme 35. Enantioselective bromoamination of allyl aniline using NBS catalyzed by BINAP(S)

图式36. 多功能苯基环烯烃的不对称溴胺化环化

Scheme 36. Asymmetric bromoamination cyclization of multifunctional phenylcyclic olefins

图式37. 采用高价碘(III)的GAP法进行的立体选择性溴胺化反应

Scheme 37. Stereoselective bromoamination via GAP method of high-valent iodine(III)

图式38. 硫代海因催化不饱和烯烃的对映选择性碘胺化反应

Scheme 38. Enantioselective iodoamination of unsaturated olefins catalyzed by thiohydantoin

图式39. 对映选择性烯烃碘胺化法合成手性环脲

Scheme 39. Stereoselective alkene iodoamination for the synthesis of chiral cyclic ureas

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