过渡金属催化硅杂环丁烷的C—Si键断裂反应研究进展

doi:10.6023/cjoc202306019

摘要/Abstract

鉴于各类有机硅化合物在材料科学、电子器件及医药研究中的广泛应用, 发展绿色高效的方法合成结构复杂的有机硅化合物具有重要意义. 硅杂环丁烷作为小环化合物, 固有的环张力和路易斯酸性使其具有特殊的反应活性, 在过渡金属催化下可发生C—Si键断裂生成Si—M活性物种, 进而实现复杂有机硅化合物的高效构筑, 因此备受关注. 基于此, 总结了近年来Rh、Pd及Ni催化硅杂环丁烷的C—Si键断裂反应, 并对反应的机理及发展趋势进行了简单讨论.

关键词: 过渡金属催化, 硅杂环丁烷, C—Si键断裂

Due to the widespread application of various organosilicon compounds in material science, electronic devices and pharmaceutical research, it is of great significance to develop green and efficient synthetic methods for diverse silicon-con- taining molecules. Silacyclobutane is an important kind of small-membered rings, which exhibits unique reactivities under transition metal catalysis to cleave the C—Si bond driven by the inherent ring strain and Lewis acidity. The resulting Si—M species can then be transformed into various organosilicon compounds. Herein, the recent advances of Pd, Rh, and Ni-catalyzed C—Si bond cleavage reactions of silacyclobutanes are summarized in detail, and the mechanism and development tendency of such reactions are briefly discussed.

Key words: transition metal catalysis, silacyclobutane, C—Si bond cleavage

引用此文

刘敏, 亓丽萍, 赵东兵. 过渡金属催化硅杂环丁烷的C—Si键断裂反应研究进展[J]. 有机化学, 2023, 43(10): 3508-3525.

Min Liu, Liping Qi, Dongbing Zhao. Recent Advances in Transition Metal-Catalyzed C—Si Bond Cleavage of Silacyclobutanes[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3508-3525.

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图/表 38

图1. 部分具有药用价值的含硅化合物

Figure 1. Examples of silicon-containing molecules of medicinal interest

图式1. 过渡金属催化硅杂环丁烷的C—Si键断反应

Scheme 1. Transition metal catalyzed C—Si bond cleavage of silacyclobutanes

图式2. Pd催化硅杂环丁烷与缺电子炔烃的扩环反应

Scheme 2. Pd-catalyzed ring expansion reaction of silacyclobutanes with electron deficient alkynes

图式4. Pd催化硅杂环丁烷与炔烃的分子内对映选择性扩环反应

Scheme 4. Pd-catalyzed a asymmetric intramolecular ring expansion reaction of silacyclobutanes with alkynes

图式5. Pd催化硅杂环丁烷与炔烃的分子间对映选择性扩环反应

Scheme 5. Pd-catalyzed asymmetric intermolecular ring expansion reaction of silacyclobutanes with alkynes

图式6. Pd催化多取代硅杂环丁烷与炔烃的扩环反应

Scheme 6. Pd-catalyzed ring expansion reaction of polysubstituted silacyclobutanes with alkynes

图式7. Rh催化硅杂环丁烷与末端的分子间扩环反应

Scheme 7. Rh-catalyzed intermolecular ring expansion reaction of silacyclobutanes with terminal alkynes

图式8. (-)-sila-mesembranol的不对称全合成

Scheme 8. Asymmetric total synthesis of (-)-sila-mesembranol

图式9. Rh催化具有螺环结构的硅杂环丁烷与炔烃的不对称双扩环反应

Scheme 9. Rh-catalyzed asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes

图式10. Rh催化4/5-螺硅杂芴与炔烃的不对称扩环反应

Scheme 10. Rh-catalyzed asymmetric ring expansion of 4/5- spirosilafluorenes with alkynes

图式11. Rh催化硅杂环丁烷与非对称活化炔烃的扩环反应

Scheme 11. Rh-catalyzed ring expansion reaction of silacyclobutanes with unsymmetrical activated alkynes

图式12. Ni催化(苯并)硅杂环丁烷与炔烃的多样性转化

Scheme 12. Ni-catalyzed divergent reactions of silacyclobutanes with alkynes

图式13. Pd催化硅杂环丁烷与环丙烯的分子间扩环反应

Scheme 13. Pd-catalyzed intermolecular ring expansion reaction of silacyclobutanes with cyclopropenes

图式14. Pd催化硅杂环丁烷与联烯酸酯的分子间扩环反应

Scheme 14. Pd-catalyzed intermolecular ring expansion reaction of silacyclobutanes with allenoates

图式15. Ni催化苯并硅杂环丁烷与亚甲基环丙烷的扩环反应

Scheme 15. Ni-catalyzed ring expansion reaction of benzosilacyclobutanes with ethyl cyclopropylideneacetate

图式16. Pd催化硅杂环丁烷与烯酮的分子间扩环反应

Scheme 16. Pd-catalyzed intermolecular ring expansion reaction of silacyclobutanes with enones

图式17. Ni催化(苯并)硅杂环丁烷与醛的扩环反应

Scheme 17. Ni-catalyzed ring expansion reaction of (benzo)- silacyclobutanes with aldehydes

图式18. Ni催化硅杂环丁烷与醛的不对称扩环反应

Scheme 18. Ni-catalyzed asymmetrical ring expansion reaction of silacyclobutanes with aldehydes

图式19. Ni催化(苯并)硅杂环丁烷与酰基硅烷的扩环反应

Scheme 19. Ni-catalyzed ring expansion reaction of (benzo)silacyclobutanes with acylsilanes

图式20. Ni催化苯并硅杂环丁烷衍生物与CO2的区域选择性插入反应

Scheme 20. Ni-catalyzed site- and regio-selective incorporation of CO2 into the benzosilacyclobutenes

图式21. Pd催化硅杂环丁烷与卡宾的分子间扩环反应

Scheme 21. Pd-catalyzed intermolecular ring expansion reaction of silacyclobutanes with carbenes

图式22. Pd催化苯并硅杂环丁烷与卡宾的分子间扩环反应

Scheme 22. Pd-catalyzed intermolecular ring expansion reaction of benzosilacyclobutanes with carbenes

图式23. Pd催化硅杂环丁烷与酰氯的扩环反应

Scheme 23. Pd-catalyzed ring expansion reaction of silacyclobutanes with acyl chlorides

图式24. Pd催化硅杂环丁烷与有机卤化物、CO的三组分反应

Scheme 24. Pd-catalyzed three-component reaction of silacyclobutanes with organic halides and CO

图式25. Pd催化硅杂环丁烷与酸酐的扩环反应

Scheme 25. Pd-catalyzed ring expansion reaction of silacyclobutanes with acid anhydrides

图式26. Pd催化硅杂环丁烷的Hiyama-Denmark偶联反应

Scheme 26. Pd-catalyzed Hiyama-Denmark coupling reaction of silacyclobutanes

图式27. (苯并)硅杂环丁烷与(苯并)环丁烷的交叉二聚反应

Scheme 27. Pd-catalyzed cross dimerization of (benzo)silacy- clobutanes with (benzo)cyclobutanes

图式28. (苯并)硅杂环丁烷与环丙烯酮及亚联苯的交叉二聚反应

Scheme 28. Pd-catalyzed cross dimerization of (benzo)silacy- clobutanes with cycolpropenones or biphenylenes

图式29. Pd催化硅杂环丁烷与2-碘代联苯衍生物的[4＋4]环加成反应

Scheme 29. Pd-catalyzed [4＋4] cycloaddition of silacyclobutanes with 2-iodobiphenyls

图式30. Ni 催化硅杂环丁烷与炔烃的对映选择性开环反应

Scheme 30. Ni-catalyzed enantioselective ring opening reaction of silacyclobutanes with alkynes

图式31. Ni催催化烯烃与硅杂环丁烷衍生物的硅基化反应

Scheme 31. Ni-catalyzed silylation of alkenes with silacyclobutanes

图式32. Ni催化硅杂环丁烷与烯烃的分子内扩环反应

Scheme 32. Ni-catalyzed intramolecular ring expansion reaction of silacyclobutanes with alkenes

图式33. Rh催化硅杂环丁环与C—H键的分子内硅基化反应

Scheme 33. Rh-catalyzed intramolecular silylation between C—H bond and silacyclobutanes

图式34. Rh催化C—H键与硅杂环丁烷之间的不对称分子内硅基化反应

Scheme 34. Rh-catalyzed asymmetric intramolecular C—H silylation of silacyclobutanes

图式35. Rh催化C—H键的对映选择性硅基化反应

Scheme 35. Rh-catalyzed C—H bond enantioselective silylation

图式36. Rh催化炔烃的C(sp)—H键的硅基化反应

Scheme 36. Rh-catalyzed silylation of C(sp)—H bond

图式37. Ni催化硅杂环丁烷与氢硅烷的氢转移反应

Scheme 37. Ni-catalyzed hydrogen transfer reaction of silacyclobutanes with hydrosilanes

图式38. Ni催化硅杂环丁烷与醛的开环反应

Scheme 38. Ni-catalyzed ring open reaction of silacyclobutanes with aryl iodides

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