Advances in the Synthesis of Organogermaniums Based on the Addition Reactions of Alkenes and Alkynes

doi:10.6023/cjoc202401014

Abstract

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

Cite this article

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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Fig. & Tab. 47

Figure 1. Common organogermanium precursors

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

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

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

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

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

Scheme 6. Iron-catalyzed germyl-functionalization of alkenes

Scheme 7. A proposed reaction mechanism

Scheme 8. Three-component germyl peroxidation of alkenes

Scheme 9. Three-component germyl azidation of alkenes

Scheme 10. Electrochemical radical germyl-oxygenation of acrylonitrile

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

Scheme 12. Pt-catalyzed hydrogermylation of cyclopropenes

Scheme 13. Iron-catalyzed hydrogermylation of styrenes with triethylgermanium

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

Scheme 15. Cu-catalyzed enantioselective hydrogermylation of alkenes

Scheme 16. Au/TiO2-catalyzed hydrogermylation of allenes

Scheme 17. Ni-catalyzed reductive alkylgermylation of alkenes

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

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

Scheme 20. Possible products in the hydrogermylation of terminal alkynes

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

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

Scheme 23. Hydrogermylation of 5-ethynyluracil nucleosides

Scheme 24. Germyl-functionalization of ynamides and its derivatives

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

Scheme 26. Visible-light-promoted germylation of propiolamides

Scheme 27. Light-promoted germylation of alkynoates

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

Scheme 29. Pd-catalyzed hydrogermylation of alkynes in water

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

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

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

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

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

Scheme 35. Ru-catalyzed hydrogermylation of internal alkynes

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

Scheme 37. Selective hydrogermylation of α-CF3 alkynes

Scheme 38. Pd-catalyzed selective hydrogermylation of ynamides

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

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

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

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

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

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

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

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

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