过渡金属催化C—H键硅基化反应构建硅杂环研究进展

doi:10.6023/cjoc202406022

摘要/Abstract

硅杂环是含硅功能分子中非常重要的结构单元, 在合成化学、药物化学和材料化学等领域具有的广泛应用, 发展结构多样化硅杂环的高效合成新方法对推动其应用研究具有重要意义. 其中, 过渡金属催化C—H键直接硅基化具有高原子经济性和步骤经济性的特点, 目前已成为构建结构复杂的硅杂环化合物的一种重要方法. 总结了近年来过渡金属催化C(sp²)—H键和C(sp³)—H键硅基化反应构筑硅杂环的研究进展.

关键词: 硅杂环, 过渡金属, C—H键活化, 硅基化, 有机硅化合物

Silacycles are essential structural motifs in silicon-containing functional molecules, which are widely used in the fields of synthetic chemistry, pharmaceutical and material science. As such, the development of efficient synthetic methods for these structurally diverse scaffolds is of great significance. Among these, due to its high atomic economy and step economy properties, transition-metal-catalyzed direct C—H silylation provides a powerful and straightforward synthetic method to form diverse silacycles. In this review, the recent progress in the construction of silacycles by transition-metal-catalyzed C(sp²)—H and C(sp³)—H silylation reactions is summarized.

Key words: silacycles, transition-metal, C—H activation, silylation, organosilicon compounds

引用此文

刘泽水, 郭桢桢, 牛俊龙. 过渡金属催化C—H键硅基化反应构建硅杂环研究进展[J]. 有机化学, 2025, 45(2): 423-447.

Zeshui Liu, Zhenzhen Guo, Junlong Niu. Recent Progress in the Construction of Silacycles by Transition- Metal-Catalyzed C—H Silylation[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 423-447.

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图/表 44

图1. 代表性的含硅功能分子

Figure 1. Representative silicon-containing functional molecules

图式1. 铂催化的分子内Si—H/C(sp2)—H脱氢偶联反应

Scheme 1. Pt-catalyzed intramolecular Si—H/C(sp2)—H dehydrogenative coupling

图式2. 镍催化烯烃的硅氢化/铱催化的脱氢硅基化反应

Scheme 2. Ni-catalyzed hydrosilylation of styrene, followed by the Ir-catalyzed dehydrogenative silylation

图式3. 铑催化的脱氢硅基化反应构建9-硅杂芴

Scheme 3. Synthesis of silafluorenes by Rh-catalyzed dehydrogenative silylation

图式4. 铑催化的脱氢硅基化反应构建硅杂螺烯化合物

Scheme 4. Synthesis of silahelicenes by Rh-catalyzed dehydrogenative silylation

图式5. 铑催化的两次脱氢硅基化反应构建轴手性螺硅杂芴

Scheme 5. Rh-catalyzed synthesis of chiral spiro-9-silabifluorenes by double dehydrogenative silylation

图式6. 铑催化硅杂环丁烷的分子内C(sp2)—H硅基化构建硅杂芴

Scheme 6. Rh-catalyzed intramolecular C(sp2)—H silylation by using silacyclobutane as the silylation reagent

图式7. 铑催化硅杂环丁烷的去对称化/脱氢硅基化构建手性硅杂芴

Scheme 7. Rh-catalyzed desymmetrization/dehydrogenative silylations of silacyclobutanes to access chiral silafluorenes

图式8. 铑催化的不对称脱氢偶联/烯烃氢硅化串联反应构建手性硅杂芴

Scheme 8. Construction of chiral silafluorenes by Rh-catalyzed tandem enantioselective dehydrogenative coupling/alkene hydrosilylation

图式9. 铑催化的不对称脱氢偶联构建硅中心手性单氢硅烷

Scheme 9. Construction of Si-stereogenic monohydrosilanes by Rh-catalyzed asymmetric dehydrogenative coupling

图式10. 铑催化的不对称脱氢硅基化反应合成手性苯并硅杂茂金属

Scheme 10. Rh-catalyzed asymmetric dehydrogenative silylation to access chiral benzosilolometallocenes

图式11. 铑或铱催化的C(sp2)—H硅基化反应构建五元苯并硅氧杂环化合物

Scheme 11. Rh- or Ir-catalyzed C(sp2)—H silylation to access 5-membered cyclic silyl ethers

图式12. 铱催化的不对称C(sp2)—H硅基化反应构建手性硅氧杂环

Scheme 12. Ir-catalyzed asymmetric C(sp2)—H silylation to access chiral cyclic silyl ethers

图式13. 铱催化胺基导向的C(sp2)—H键硅基化反应

Scheme 13. Ir-catalyzed C(sp2)—H silylation directed by an amine

图式14. 铑催化苄醇、亚胺与硅烷的不对称[4＋1]环化反应构建硅中心手性硅杂环

Scheme 14. Rh-catalyzed asymmetric [4＋1] cyclization of benzyl alcohols and benzaldimines with silane to access silicon-stereogenic heterocycles

图式15. 铱催化的分子内C(sp2)—H硅基化反应构建非对称的二硅氧杂环

Scheme 15. Ir-catalyzed intramolecular C(sp2)—H silylation to access unsymmetrical cyclic disiloxanes

图式16. 钯催化的两次C(sp2)—H硅基化反应构建二硅氧杂环化合物

Scheme 16. Pd-catalyzed twofold C(sp2)—H silylation to access cyclic disiloxanes

图式17. 时间控制的钯催化C(sp2)—H活化发散性合成硅杂环化合物

Scheme 17. Time-controlled Pd-catalyzed divergent synthesis of silacycles via C(sp2)—H activation

图式18. 钯催化C(sp2)—H活化/Brook重排/逆Brook重排串联反应合成硅杂环化合物

Scheme 18. Pd-catalyzed synthesis of diverse silacycles via C(sp2)—H activation/Brook- and retro-Brook-type rearrangement cascade

图式19. 钌催化的两次C(sp2)—H硅基化反应构建吲哚稠合苯并噻咯化合物

Scheme 19. Ru-catalyzed synthesis of indole-fused benzosiloles by 2?fold electrophilic C(sp2)—H silylation

图式20. 铑催化的分子内C(sp2)—H硅基化反应构建苯并六元硅氧杂环

Scheme 20. Rh-catalyzed intramolecular C(sp2)—H silylation to access six-membered phenoxasilines

图式21. 铱催化的分子内C(sp2)—H硅基化反应构建六元二硅氧杂环

Scheme 21. Ir-catalyzed intramolecular C(sp2)—H silylation to access six-membered cyclic disiloxanes

图式22. 铑催化2-芳基苯酚衍生物的硅基化反应构建二苯并硅氧杂环

Scheme 22. Construction of six-membered π-conjugated dibenzooxasilines via Rh-catalyzed silylation

图式23. 铑催化的不对称脱氢偶联构建硅中心手性六元硅杂环化合物

Scheme 23. Rh-catalyzed asymmetric dehydrogenative coupling for the construction of six-membered Si-stereogenic heterocycles

图式24. 聚合物负载铱催化的分子间脱氢偶联构建六元硅杂环化合物

Scheme 24. POP-supported Ir-catalyzed intermolecular dehydrogenative coupling for the construction of six-membered oxasilacycles

图式25. 铱催化的分子内脱氢偶联构建七元硅杂环化合物

Scheme 25. Ir-catalyzed intramolecular dehydrogenative coupling for the construction of seven-membered silacycles

图式26. 钯催化的分子间C(sp2)—H硅基化反应构建二苯并七元硅杂环化合物

Scheme 26. Pd-catalyzed intermolecular C(sp2)—H silylation for the construction of seven-membered silacycles

图式27. 铑催化的不对称脱氢偶联构建硅中心手性七元硅杂环化合物

Scheme 27. Rh-catalyzed asymmetric dehydrogenative coupling for the construction of seven-membered Si-stereogenic heterocycles

图式28. 钯催化的分子内C(sp2)—H硅基化合成七元硅杂环化合物

Scheme 28. Pd-catalyzed intramolecular C(sp2)—H silylation for the construction of seven-membered silacycles

图式29. 钯催化杂环丁烷与2-碘联苯类化合物的环化反应构建八元硅杂环

Scheme 29. Pd-catalyzed annulation of silacyclobutanes and 2?iodobiarenes to access eight-membered silacycles

图式30. 钯催化的分子内邻位或远程C(sp2)—H硅基化合成十元硅杂环化合物

Scheme 30. Pd-catalyzed intramolecular ortho- or remote-C(sp2)—H silylation for the construction of ten-membered silacycles

图式31. 铂催化的分子内Si—H/C(sp3)—H脱氢偶联反应

Scheme 31. Pt-catalyzed intramolecular Si—H/C(sp3)—H dehydrogenative coupling

图式32. 羟基导向铱催化的非活化C(sp3)—H键官能团化反应

Scheme 32. Ir-catalyzed functionalization of unactivated C(sp3)—H directed by an alcohol

图式33. 胺基导向铱催化的一级C(sp3)—H键硅基化反应

Scheme 33. Ir-catalyzed primary C(sp3)—H silylation directed by an amine

图式34. 铱催化的分子内未活化C(sp3)—H硅基化构建五元硅杂环

Scheme 34. Ir-catalyzed intramolecular unactivated C(sp3)—H silylation for the construction of five-membered silacycles

图式35. 铑催化的分子内未活化C(sp3)—H硅基化构建五元硅杂环

Scheme 35. Rh-catalyzed intramolecular unactivated C(sp3)—H silylation for the construction of five-membered silacycles

图式36. 铱催化分子内未活化C(sp3)—H对映选择性硅基化构建手性五元硅杂环

Scheme 36. Ir-catalyzed intramolecular unactivated C(sp3)—H enantioselective silylation for the construction of chiral five-membered silacycles

图式37. 钌催化分子内C(sp3)—H脱氢硅基化反应构建多样性五元硅杂环

Scheme 37. Ru-catalyzed intramolecular C(sp3)—H dehydrogenative silylation to access diverse five-membered silacycles

图式38. 铑催化分子内未活化C(sp3)—H对映选择性硅基化构建手性五元硅杂环

Scheme 38. Rh-catalyzed intramolecular unactivated C(sp3)—H enantioselective silylation for the construction of chiral five-membered silacycles

图式39. 铑催化环丙烷C(sp3)—H对映选择性硅基化构建手性硅杂环

Scheme 39. Rh-catalyzed cyclopropyl C(sp3)—H enantioselective silylation for the construction of chiral silacycles

图式40. 铑催化苄位C(sp3)—H硅基化构建六元硅杂环

Scheme 40. Rh-catalyzed benzyl C(sp3)—H silylation for the construction of six-membered silacycles

图式41. 铑催化叔醇非活化C(sp3)—H键硅基化反应

Scheme 41. Rh-catalyzed unactivated C(sp3)—H silylation of tertiary alcohols

图式42. 铑催化不对称C(sp3)—H/Si—H脱氢偶联构建具有轴手性和硅手性的七元硅杂环

Scheme 42. Rh-catalyzed asymmetric C(sp3)—H/Si—H dehydrogenative coupling for the construction of seven-membered silacycles containing both silicon-central and axial chiralities

图式43. 钯催化的分子间C(sp3)—H硅基化反应构建七元硅杂环化合物

Scheme 43. Pd-catalyzed intermolecular C(sp3)—H silylation for the construction of seven-membered silacycles

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