砜亚胺N-芳基化的研究进展及其应用

doi:10.6023/cjoc202110011

摘要/Abstract

砜亚胺是有机合成中一类重要的结构单元, 可用作手性助剂、手性配体及有机催化剂等, 也是构建杂环化合物的关键中间体. 因其具有独特的生物活性, 在医药与农药方面也得到了广泛应用. 鉴于砜亚胺在有机化学以及药物研发中的重要作用, 其合成方法备受关注. 其中, 用NH-砜亚胺芳基化策略制备N-芳基砜亚胺的方法, 由于具有原子经济高、条件温和及反应路线短等优势, 受到了化学家越来越多的关注, 并取得了长足的进步. 系统介绍了NH-砜亚胺通过C—N键的构建来合成N-芳基砜亚胺的各类方法, 及其在有机合成方面的应用.

关键词: NH-砜亚胺, N-芳基化, N-芳基-砜亚胺, C—N交叉偶联

Sulfoximines represent an important structural motif in organic chemistry, and have been utilized as chiral auxiliaries, chiral ligands and organocatalysts. They also serve as key intermediates for the construction of heterocyclic compounds. Attributing to their unique bioactivities, sulfoximines have been developed as previliged pharmacophores and widely used in pharmaceutical chemistry and agriculture. Considering the wide applications, the synthetic methods to afford sulfoximines have attracted increasing attention. Among them, the direct arylation of NH-sulfoximines to prepare NAr- sulfoxmines exhibites some unique advantages, including atom-economics, mild conditions and step-economics, and thus has made tremedous progress in recent years. Various methods of NH-sulfoximines to afford NAr-sulfoximines via a C—N bond formation strategy, as well as their applications in synthesis of bioactive molecules and ligands for transition-metal catalysts, are reviewed.

Key words: NH-sulfoximine, N-arylation, NAr-sulfoximine, C—N bond formation

引用此文

李雪, 王聪, 贾铁争. 砜亚胺N-芳基化的研究进展及其应用[J]. 有机化学, 2022, 42(3): 714-731.

Xue Li, Cong Wang, Tiezheng Jia. Recent Advances in N-Arylation of NH-Sulfoximines and Their Applications[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 714-731.

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图/表 22

图式1. 具有重要生物活性砜亚胺的代表实例

Scheme 1. Representative examples of bioactive sulfoximines

图式2. 钯催化NH-砜亚胺与芳基溴化物的N-芳基化反应机理

图式3. 一锅两步法制备N-芳基砜亚胺

Scheme 3. One-pot-two-steps synthesis of N-arylated sulfoximines

图式4. 铜催化唑类和多氟芳烃与NH-砜亚胺的直接芳基化反应

Scheme 4. Copper-catalyzed direct arylation of NH-sulfoximines with azoles and polyfluoroarenes

图式5. NH-砜亚胺与8-氨基喹啉衍生的苯甲酰胺的N-芳基化反应机理

图式6. NH-砜亚胺与芳基硼酸的Chan-Lam偶联反应机理

Scheme 6. Proposed mechanism for Chan-Lam coupling of NH- sulfoximine and arylboronic acid

图式7. 无外加氧化剂条件下NH-砜亚胺与芳基硼酸Chan-Lam偶联反应的机理

图式8. NH-砜亚胺与过氧化苯甲酰N-芳基化的反应机理

图式9. 电氧化还原镍催化NH-砜亚胺与芳基溴化物的N-芳基化反应机理

图式10. 光-钴双重催化NH-砜亚胺与富电子烯烃N-芳基化的机理

图式11. 一锅一步法合成苯并噻嗪

Scheme 11. One-pot one-operation synthesis of benzothiazine

图式12. 钯催化1,3-二苯基烯丙基乙酸酯与丙二酸二甲酯的不对称烯丙基化反应

Scheme 12. Palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenylallyl acetates with dimethyl malonate

图式13. 双砜亚胺配体的合成路径

Scheme 13. Synthetic route of bis(sulfoximine) ligand

图式14. 铜催化HDA反应

Scheme 14. Copper-catalyzed hetero-Diels-Alder reactions

图式15. 铜催化不对称Mukaiyama羟醛缩合

Scheme 15. Copper-catalyzed asymmetric Mukaiyama-aldol reactions

图式16. 氨基砜亚胺手性配体的合成途径

Scheme 16. Synthetic route of aminosulfoximine ligands

图式17. Ir催化不对称亚胺氢化反应

Scheme 17. Ir-catalyzed asymmetric imine hydrogenation

图式18. [Ir(cod)(100-102a-c)]BArF催化前体的合成方法

Scheme 18. Synthesis of [Ir(cod)(100-102a-c)]BArF catalyst precursors

图式19. 弱配位取代基连接的烯烃的不对称氢化

Scheme 19. Asymmetric hydrogenation of olefins tethering poorly coordinative groups

图式20. 基于砜亚胺加成策略构建苄位手性中心的方法

Scheme 20. Synthesis of stereogenic center at benzylic position via a sulfoximine addition strategy

图式21. 3,4-二氢喹啉2(1H)-酮(117)合成路径

Scheme 21. Synthetic route of 3,4-dihydroquinolin-2(1H)-one (117)

图式22. 4-氨基苯并噻嗪立体选择性合成的底物范围

Scheme 22. Substrate scope for stereoselective synthesis of 4-aminobenzothiazines Reaction conditions: (a) 5 mol% Pd2(dba)3, 7.5 mol% Xanthphos, 2.0 equiv. Cs2CO3, 1,4-dioxane, 100 oC, 2 h; (b) 2.0 equiv. LiHMDS (1 mol/L in THF), –78 oC, 2 h; (c) HCl (4 mol/L in 1,4-dioxane), MeOH, 0 oC, 2 h.

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