动力学拆分在催化不对称1,3-偶极环加成反应中的研究进展

doi:10.6023/cjoc202205037

摘要/Abstract

动力学拆分是一类高效且应用广泛的不对称有机合成策略, 可将外消旋化合物转化成高光学活性的构筑模块, 是现代不对称合成领域的重要组成部分. 尽管多年前就已被报道, 但涉及不对称催化的动力学拆分过程在实际运用中往往拆分效率较低或者底物适用范围较窄, 这极大地阻碍了该策略的发展. 过去的二十年里, 随着不对称催化领域中手性催化剂和手性配体的快速发展, 动力学拆分策略开始广泛运用于外消旋底物的高效分离, 进而获得优异光学纯度的手性分子. 自2005年亚甲胺亚胺通过催化不对称1,3-偶极环加成反应实现动力学拆分的案例被首次报道以来, 利用1,3-偶极环加成反应以实现高效动力学拆分获取手性氮杂环化合物或高对映选择性片段的相关研究已得到较好发展. 根据参与的1,3-偶极子的不同, 总结了近年来动力学拆分策略在亚甲胺亚胺和亚甲胺叶立德参的催化不对称1,3-偶极环加成反应中的研究进展, 并讨论了相关局限性和发展前景.

关键词: 动力学拆分, 不对称1,3-偶极环加成, 亚甲胺亚胺, 亚甲胺叶立德, 手性氮杂环

Kinetic resolution is an efficient and widely used asymmetric organic synthesis strategy, which can transform racemic compounds into highly optically active building blocks. It is quite an important part of modern asymmetric synthesis. Although it has long been known as a common method to gain enantioenriched raw material, kinetic resolution processes involving asymmetric catalysis often show poor resolution efficiency and limited substrates scope in practice, which greatly hinder the development of this strategy. It is not until the past two decades, with the rapid development of chiral ligands and catalysts in the field of asymmetric catalysis, that kinetic resolution strategy has been increasingly applied in the efficient separation of racemic substrates to provide versatile chiral molecules with excellent optical purity. Since the strategy of kinetic resolution was first successfully employed in the catalytic asymmetric 1,3-dipolar cycloadditions with azomethine imines in 2005, studies on 1,3-dipolar cycloadditions with efficient kinetic resolution to achieve chiral N-heterocyclic compounds or highly enantioselective fragments have been well developed. The recent progress of kinetic resolution strategy in catalytic asymmetric 1,3-dipolar cycloaddition reactions involving azomethine imines and azomethine ylides is summarized according to the different azomethine 1,3-dipoles involved, and the related limitations and development prospects are also discussed.

Key words: kinetic resolution, asymmetric 1,3-dipolar cycloaddition, azomethine imine, azomethine ylide, chiral N-heterocycle

引用此文

刘华超, 沈冲, 常鑫, 王春江. 动力学拆分在催化不对称1,3-偶极环加成反应中的研究进展[J]. 有机化学, 2022, 42(10): 3322-3334.

Huachao Liu, Chong Shen, Xin Chang, Chunjiang Wang. Recent Advances in Catalytic Asymmetric 1,3-Dipolar Cycloaddition Reactions with Kinetic Resolution[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3322-3334.

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图/表 16

图式1. 动力学拆分原理及反应平衡点

Scheme 1. Principle and equilibrium point of kinetic resolution

图式2. 铜催化不对称[3+2]环加成反应实现亚甲胺亚胺的动力学拆分

Scheme 2. Kinetic resolution of azomethine imines via copper (I)-catalyzed asymmetric [3+2] cycloadditions

图式3. 氮杂环卡宾催化不对称[3+4]环加成反应实现亚甲胺亚胺的动力学拆分

Scheme 3. N-Heterocyclic carbene-catalyzed asymmetric [3+4] cycloadditions with azomethine imines by kinetic resolution

图式4. 铜催化现场生成氮杂二烯的不对称[3+4]环加成反应实现亚甲胺亚胺的动力学拆分

Scheme 4. Copper(II)-catalyzed enantioselective [3+4] cycloadditions of in situ formed azoalkenes with azomethine imines involving kinetic resolution strategy

图式5. 银催化缺电子异氰不对称[3+3]环加成反应完成亚甲胺亚胺的动力学拆分

Scheme 5. Silver(I)-catalyzed enantioconvergent [3+3] cycloadditions of electron-deficient isocyanides realizing kinetic resolution of racemic azomethine imines

图式6. 氨基硫脲催化剂催化3-硝基-2-氢-苯并吡喃衍生物的动力学拆分

Scheme 6. Kinetic resolution of racemic 3-nitro-2H-chromene derivatives catalyzed by amino thiourea catalyst

图式7. 手性磷酸催化外消旋2,3-联烯酯的动力学拆分

Scheme 7. Kinetic resolution of racemic 2,3-allenoates enabled by chiral phosphoric acid

图式8. 铜催化二氢吡喃酮类化合物的动力学拆分

Scheme 8. Cu(I)-catalyzed kinetic resolution of 2H-pyran-3(6H)-one compounds

图式9. 金属化亚甲胺叶立德实现托品烷衍生物的动力学拆分

Scheme 9. Kinetic resolution of tropane derivatives with N-metallated azomethine ylides

图式10. 铜(I)催化MBH羧酸酯的动力学拆分和平行动力学拆分

Scheme 10. Cu(I)-catalyzed kinetic resolution and parallel kinetic resolution of MBH acetates

图式11. Ag(I)/(S)-TF-BiphamPhos 38络合物催化环戊烯-1,3-二酮的动力学拆分

Scheme 11. Kinetic resolution of cyclopentene-1,3-diones catalyzed by Ag(I)/(S)-TF-BiphamPhos 38 complex

图式12. 金属化亚甲胺叶立德的两种常见共振式和区域选择性的1,3-偶极环加成反应

Scheme 12. Two most commonly zwitterionic resonance forms of N-metallated azomethine ylides and 1,3-dipolar cycloadditions with divergent regioselectivities

图式13. Cu(I)/(S)-TF-BiphamPhos 38络合物催化区域选择性的1,3-偶极环加成反应实现降冰片烯酮的动力学拆分

Scheme 13. Kinetic resolution of alkylidene norcamphors via Cu(I)/(S)-TF-BiphamPhos 38 complex catalyzed regioselective 1,3-dipolar cycloadditions

图式14. (+)-(Z)- and (-)-(E)-β-檀香醇关键中间体的简易合成

Scheme 14. Facile access to the key intermediate of (+)-(Z)- and (-)-(E)-β-santalol

图式15. 铜(I)催化exo-和endo-双环戊二烯酮的动力学拆分

Scheme 15. Cu(I)-catalzyed kinetic resolution of exo- and endo-3-oxodicyclopentadienes

图式16. 铜催化外消旋氮杂环丙烯的动力学拆分

Scheme 16. Cu-catalyzed kinetic resolution of racemic 2H-azirines

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