基于烯烃和炔烃的加成反应合成有机锗化合物的研究进展

doi:10.6023/cjoc202401014

摘要/Abstract

有机锗化合物具有广泛的潜在应用价值, 尤其在有机合成、药物化学和材料科学领域. 然而, 相较于其他碳族元素化学, 有机锗化学的研究和发展长期以来相对零散和缓慢, 近几年却越来越受到人们的关注. 介绍通过烯烃和炔烃的加成反应合成有机锗化合物的研究进展, 并按照锗与烯烃和炔烃的加成反应类型进行分类, 重点介绍不同反应体系、反应机理以及合成方法. 此外, 对于研究过程中遇到的问题及未来的发展趋势也进行了展望.

关键词: 有机锗, 烯烃, 炔烃, 氢锗化, 加成反应

Organogermanium compounds have a wide range of potential applications, especially in the fields of organic synthesis, medicinal chemistry and materials sciences. However, compared with the progress of other elements of the carbon family, the study and development of organogermanium chemistry have long been relatively scattered and sluggish, although it has attracted increasing attention from chemists in recent years. This review aims to introduce the research progress in the synthesis of organogermanium compounds via the addition reactions of alkenes and alkynes. The progress is classified according to the types of addition reactions of germanium with alkenes and alkynes, different reaction systems, reaction mechanisms and synthetic protocols. In addition, the problems encountered during the research process and future development trends are also prospected.

Key words: organogermanium, alkene, alkyne, hydrogermylation, addition reaction

引用此文

吕雷阳, 罗亚妮, 李志平. 基于烯烃和炔烃的加成反应合成有机锗化合物的研究进展[J]. 有机化学, 2024, 44(7): 2092-2109.

Leiyang Lv, Yani Luo, Zhiping Li. Advances in the Synthesis of Organogermaniums Based on the Addition Reactions of Alkenes and Alkynes[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2092-2109.

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图/表 47

图1. 常用的有机锗前体

Figure 1. Common organogermanium precursors

图式1. 烯烃/炔烃的加成反应制备有机锗化合物总结

Scheme 1. Summary of the preparation of organogermaniums via addition reactions of alkenes or alkynes

图式2. 早期关于有机锗与烯烃的自由基加成反应的研究

Scheme 2. Early studies on the radical addition reactions of organogermaniums with alkenes

图式3. Et3B/O2诱导的烯烃/烯醇硅醚的氢锗化反应

Scheme 3. Et3B/O2-induced hydrogermylation of alkenes and silyl enol ethers

图式4. 光催化锗基羧酸脱羧与苯乙烯的加成反应

Scheme 4. Photocatalytic decarboxylative addition reactions of germacarboxylic acids with styrene

图式5. 光催化氢原子转移诱导的烯烃氢锗化反应

Scheme 5. Hydrogermylation of alkenes via organophotoredox- initiated HAT catalysis

图式6. 铁催化烯烃的锗化-官能团化反应

Scheme 6. Iron-catalyzed germyl-functionalization of alkenes

图式7. 可能的反应机理

Scheme 7. A proposed reaction mechanism

图式8. 烯烃三组分反应合成锗基过氧化物

Scheme 8. Three-component germyl peroxidation of alkenes

图式9. 烯烃三组分反应合成锗基叠氮化物

Scheme 9. Three-component germyl azidation of alkenes

图式10. 电化学参与的丙烯腈自由基锗化氧化反应

Scheme 10. Electrochemical radical germyl-oxygenation of acrylonitrile

图式11. 过渡金属催化锗烷与烯烃的反马氏加成

Scheme 11. Transition metal-catalyzed anti-Markovnikov addition of hydrogermanes with alkenes

图式12. Pt催化环丙烯的氢锗化反应

Scheme 12. Pt-catalyzed hydrogermylation of cyclopropenes

图式13. Fe催化三乙基锗与苯乙烯的氢锗化反应

Scheme 13. Iron-catalyzed hydrogermylation of styrenes with triethylgermanium

图式14. Pd催化烯基芳基碘的双锗化反应

Scheme 14. Pd-catalyzed digermanylation of alkene tethered aryl iodides

图式15. Cu催化烯烃的不对称氢锗化反应

Scheme 15. Cu-catalyzed enantioselective hydrogermylation of alkenes

图式16. Au/TiO2催化联烯的氢锗化反应

Scheme 16. Au/TiO2-catalyzed hydrogermylation of allenes

图式17. 镍催化烯烃的还原烷基锗化反应

Scheme 17. Ni-catalyzed reductive alkylgermylation of alkenes

图式18. 镍催化三组分还原偶联反应

Scheme 18. Ni-catalyzed three-component reductive cross- coupling reactions

图式19. B(C6F5)3催化烯烃的转移氢锗化反应

Scheme 19. B(C6F5)3-catalyzed transfer hydrogermylation of alkenes

图式20. 末端炔烃氢锗化反应可能的产物

Scheme 20. Possible products in the hydrogermylation of terminal alkynes

图式21. 温度控制炔烃的Z/E选择性氢锗化反应

Scheme 21. Temperature-controlled Z/E-selective hydroger- mylation of alkynes

图式22. (TMS)3GeH与末端炔烃的氢锗化反应

Scheme 22. Hydrogermylation of terminal alkynes with (TMS)3GeH

图式23. 5-乙炔基尿嘧啶核苷的氢锗化反应

Scheme 23. Hydrogermylation of 5-ethynyluracil nucleosides

图式24. 炔酰胺及其衍生物的锗化-官能团化反应

Scheme 24. Germyl-functionalization of ynamides and its derivatives

图式25. Mn2(CO)10催化末端炔烃的氢锗化反应

Scheme 25. Mn2(CO)10-catalyzed hydrogermylation of terminal alkynes

图式26. 可见光促进炔丙基酰胺的锗化反应

Scheme 26. Visible-light-promoted germylation of propiolamides

图式27. 光促进炔丙酸酯的锗化反应

Scheme 27. Light-promoted germylation of alkynoates

图式28. Pd(PPh3)4催化末端炔烃的氢锗化反应

Scheme 28. Pd(PPh3)4-catalyzed hydrogermylation of terminal alkynes

图式29. 水相中Pd催化炔烃的氢锗化反应

Scheme 29. Pd-catalyzed hydrogermylation of alkynes in water

图式30. Co催化末端炔烃的顺式氢锗化反应

Scheme 30. Co-catalyzed cis-hydrogermylation of terminal alkynes

图式31. Au/TiO2体系催化末端炔烃的双锗化反应

Scheme 31. Au/TiO2-catalyzed digermylation of terminal alkynes

图式32. NHC-Co催化末端炔烃的马氏氢锗化反应

Scheme 32. NHC-Co-catalyzed Markovnikov hydrogermylation of terminal alkynes

图式33. B(C6F5)3催化末端炔烃的氢锗化反应

Scheme 33. B(C6F5)3-catalyzed hydrogermylation of terminal alkynes

图式34. ZnEt2介导的炔烃锗化官能团化反应

Scheme 34. ZnEt2-mediated germyl-functionalization of terminal alkynes

图式35. Ru催化内炔的氢锗化反应

Scheme 35. Ru-catalyzed hydrogermylation of internal alkynes

图式36. [Cp*RuCl]4催化内炔的反式氢锗化反应

Scheme 36. [Cp*RuCl]4-catalyzed anti-hydrogermylation of internal alkynes

图式37. α-三氟甲基炔烃的选择性氢锗化反应

Scheme 37. Selective hydrogermylation of α-CF3 alkynes

图式38. Pd催化炔酰胺的选择性氢锗化反应

Scheme 38. Pd-catalyzed selective hydrogermylation of ynamides

图式39. CpFe(CO)2(Me)催化内炔的反式氢锗化反应

Scheme 39. CpFe(CO)2(Me)-catalyzed anti-hydrogermylation of internal alkynes

图式40. Co-H催化2-炔烃的氢锗化反应

Scheme 40. Co-H-catalyzed hydrogermylation of 2-alkynes

图式41. 路易斯酸催化内炔的选择性氢锗化反应

Scheme 41. Lewis acid-catalyzed selective-hydrogermylation of internal alkynes

图式42. NaHB(sec-Bu)3催化苯乙烯衍生物的氢锗化反应

Scheme 42. NaHB(sec-Bu)3-catalyzed hydrogermylation of styrene derivatives

图式43. Ru催化1,3-二炔的串联氢锗化反应

Scheme 43. Ru-catalyzed tandem hydrogermylation of 1,3- diynes

图式44. 锌试剂介导的炔烃氢锗化合成锗杂环化合物

Scheme 44. Organozinc-mediated synthesis of germacycles via hydrogermylation of alkynes

图式45. 二异丁基氢化铝参与的合成锗杂环戊二烯

Scheme 45. (i-Bu)2AlH-mediated synthesis of germols

图式46. 萘基锂介导的环化反应合成苯并锗杂环戊二烯

Scheme 46. LiNaPh-mediated cyclization for the synthesis of benzogermols

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