不对称催化Si—H/X—H脱氢偶联构筑硅中心手性

doi:10.6023/cjoc202305001

摘要/Abstract

硅中心手性有机硅化物因其独特的结构和性质, 在有机合成、功能材料及生物医药等领域展现出特有的价值和应用前景, 受到了化学家们的广泛关注. 近年来, 构筑硅中心手性的方法得到了快速发展, 特别是利用过渡金属催化对前手性硅烷进行去对称化反应. 其中, 以二氢硅烷为底物进行的不对称催化Si—H/X—H脱氢偶联(Si-CADC), 因其具有反应简单高效、原子经济性高、结构多样性好和对映选择性高等优点, 成为了构筑硅中心手性的重要手段和方法. 根据反应类型和产物的不同, 主要从以下三个层次展开综述: (1)不对称脱氢偶联串联策略构筑四取代硅中心手性有机硅烷; (2)分子内Si—H/C—H脱氢偶联构筑环状硅中心手性单氢硅烷; (3)分子间Si—H/X—H脱氢偶联构筑非环状多样化的硅中心手性硅烷.

关键词: 硅中心手性, 有机硅化学, 二氢硅烷, 不对称催化, 脱氢偶联

Owing to its unique structure and properties, silicon-stereogenic silanes have displayed valuable application prospects in the fields of organic synthesis, functional materials and biomedicine, and have received extensive attention from chemists. In recent years, methods for the construction of silicon-stereogenic center have been rapidly developed, especially the use of transition metal catalysis to conduct the desymmetrization of prochiral silanes. Among them, asymmetric catalytic Si—H/X—H dehydrogenative coupling (Si-CADC) using dihydrosilane as the substrate has become an important approach and key technology for the construction of silicon-stereogenic center, because of its advantages of high efficiency, high atomic economy, good structural diversity and high enantioselectivity. According to the different reaction categorie and products, this review will mainly summarize and discuss in three stages: (1) asymmetric dehydrogenative coupling tandem strategy to construct tetrasubstituted silicon-stereogenic silanes, (2) intramolecular Si—H/C—H dehydrogenative coupling to construct cyclic silicon-stereogenic monohydrosilanes, and (3) intermolecular Si—H/X—H dehydrogenative coupling to construct a variety of ayclic silicon-stereogenic silanes.

Key words: silicon-stereogenic chirality, organosilicon chemistry, dihydrosilane, asymmetric catalysis, dehydrogenative coupling

引用此文

赵佳怡, 葛怡聪, 何川. 不对称催化Si—H/X—H脱氢偶联构筑硅中心手性[J]. 有机化学, 2023, 43(10): 3352-3366.

Jiayi Zhao, Yicong Ge, Chuan He. Construction of Silicon-Stereogenic Center via Catalytic Asymmetric Si—H/X—H Dehydrogenative Coupling[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3352-3366.

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图/表 21

图1. 硅立体中心功能分子

Figure 1. Si-stereogenic functional molecules

图式1. 构建硅手性的挑战

Scheme 1. Challenges to access Si-stereogenic center

图式2. 构筑硅中心手性的方法

Scheme 2. Methods to access Si-stereogenic center

图式3. 不对称催化Si—H/X—H脱氢偶联反应

Scheme 3. Catalytic asymmetric Si—H/X—H dehydrogenative coupling

图式4. 分子内不对称两次脱氢偶联构建轴手性螺硅芴

Scheme 4. Intramolecular asymmetric double dehydrogenative coupling for the construction of axially chiral spirosilabifluorene

图式5. 不对称脱氢偶联构建硅中心手性串联策略设计

Scheme 5. Design of tandem strategy for the construction of Si-stereogenic center via asymmetric dehydrogenative coupling

图式6. 串联不对称脱氢偶联/烯烃氢硅化反应构建硅中心手性硅烷

Scheme 6. Construction of Si-stereogenic silanes by tandem asymmetric dehydrogenative coupling/alkene hydrosilylation

图式7. 铑催化的串联不对称脱氢偶联/烯烃氢硅化反应机理

Scheme 7. Mechanism of Rh-catalyzed tandem asymmetric dehydrogenative coupling/alkene hydrosilylation

图式8. 串联不对称Si—H/C(sp3)—H脱氢偶联/烯烃氢硅化反应

Scheme 8. Tandem asymmetric Si—H/C(sp3)—H dehydrogenative coupling/alkene hydrosilylation

图式9. 不对称脱氢偶联构建硅中心手性一氢硅烷

Scheme 9. Asymmetric dehydrogenative coupling for the construction of Si-stereogenic monohydrosilanes

图式10. 不对称脱氢偶联构建硅中心手性六、七元硅杂环

Scheme 10. Asymmetric dehydrogenative coupling for the construction of six- and seven-membered Si-stereogenic heterocycles

图式11. 不对称Si—H/C(sp3)—H脱氢偶联同时构建轴手性和硅中心手性

Scheme 11. Asymmetric Si—H/C(sp3)—H dehydrogenative coupling for the construction of axial and Si-stereogenic chiralities

图式12. 分子间不对称Si—H/C—H脱氢偶联

Scheme 12. Intermolecular asymmetric Si—H/C—H dehydrogenative coupling

图式13. 二氢硅烷与噻吩的不对称Si—H/C—H脱氢偶联

Scheme 13. Asymmetric Si—H/C—H dehydrogenative coupling of dihydrosilanes with thiophenes

图式14. 早期不对称Si—H/O—H脱氢偶联

Scheme 14. Early examples of asymmetric Si—H/O—H dehydrogenative coupling

图式15. 不对称Si—H/O—H脱氢偶联构建硅中心手性硅醚和硅氧烷

Scheme 15. Asymmetric Si—H/O—H dehydrogenative coupling for the construction of Si-stereogenic siloxanes

图式16. 不对称催化二氢硅烷水氧化反应构建手性硅醇

Scheme 16. Catalytic asymmetric hydrolytic oxidation of dihydrosilanes for the construction of chiral silanols

图式17. 不对称催化二氢硅烷水氧化机理研究

Scheme 17. Mechanistic study of the asymmetric hydrolytic oxidation

图式18. 铜催化二氢硅烷水氧化反应

Scheme 18. Copper-catalyzed asymmetric hydrolytic oxidation of dihydrosilanes

图式19. 铜催化硅二醇不对称脱氢偶联构建手性硅醇

Scheme 19. Copper-catalyzed asymmetric dehydrogenative coupling of silanediols for the construction of chiral silanols

图式20. 不对称Si—H/N—H脱氢偶联构建硅中心手性硅氮烷

Scheme 20. Asymmetric Si—H/N—H dehydrogenative coupling for the construction of Si-stereogenic silazanes

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