X类型硅基配体介导的碳氢官能化反应

doi:10.6023/cjoc202406014

摘要/Abstract

研究和发展新型配体对于过渡金属(TM)催化具有重要意义. 随着有机硅化学的快速发展, 综述X型硅基配体参与的过渡金属催化反应这一话题非常必要且具有吸引力. 探讨了硅基配体独特的σ-供电子能力和反位效应, 阐述了它们在碳氢官能化反应中对反应活性和选择性起到的关键作用. 此外, 还对该领域未来的发展趋势进行了展望, 希望能为催化合成化学领域提供新的思路和启发.

关键词: X型硅基配体, σ-给电子特性, 反位效应, 碳氢官能化, 硼化反应, 硅化反应

The development of novel ligands for transition-metal (TM) catalysis holds significant importance. With the rapid evolution of organosilicon chemistry, summarizing the topic of X-type silyl ligands for TM catalysis is appealing and timely. The unique σ-donating characteristics and trans-effects of silyl ligands are explored, and their pivotal role in enhancing the reactivity and selectivity of C—H functionalization reactions is elucidated. Furthermore, valuable insights into future advancements in this field are also prospected, with the goal of inspiring new applications and perspectives in the realm of catalytic synthetic chemistry.

Key words: X-type silyl ligand, σ-donating characteristic, trans-effect, C—H functionalization, borylation, silylation

引用此文

高吉慧, 何川. X类型硅基配体介导的碳氢官能化反应[J]. 有机化学, 2025, 45(2): 641-654.

Jihui Gao, Chuan He. X-Type Silyl Ligands Mediated C—H Functionalization Reactions[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 641-654.

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图/表 16

图式1. L-, Z-, X-型配体

Scheme 1. L-, Z-, and X-type ligands

图式2. 硅基金属络合物的性质

Scheme 2. Properties of silyl-metal complexes

图式3. 硅基金属络合物及其催化的碳氢活化反应

Scheme 3. Representative silyl-metal complexes and its catalytic C—H functionalization reactions

图式4. 硅基金属络合物介导的芳基碳氢活化反应

Scheme 4. Silyl-metal complexes mediated aryl C—H bond activation process

图式5. 硅基金属络合物催化的芳基C(sp2)—H硼化反应

Scheme 5. Silyl-metal complexes catalyzed C(sp2)—H borylation reaction of arenes

图式6. 设计双齿L,X-型硅基配体实现区域选择性的芳基C(sp2)—H硼化反应

Scheme 6. Design of the bidentate L,X-type silyl ligands for regioselective C(sp2)—H borylation of arenes

图式7. L,X-型双齿硅基配体催化的区域选择性芳基C(sp2)—H硼化反应

Scheme 7. L,X-type silyl ligands catalyzed regioselective C(sp2)—H borylation of arenes

图式8. Pd-PSiP络合物催化的烯烃C(sp2)—H硼化反应

Scheme 8. Pd-PSiP complexes catalyzed C(sp2)—H borylation of alkenes

图式9. Ir-NNSi金属络合物催化的炔烃C(sp)—H硼化反应

Scheme 9. Ir-NNSi complexes catalyzed C(sp)—H borylation of alkynes

图式10. NSi配体催化的酰胺导向的C(sp3)—H硼化反应

Scheme 10. NSi-ligand enabled amide-directed C(sp3)—H borylation

图式11. Ir-NNSi体系催化的C(sp3)—H硼化反应

Scheme 11. Ir-NNSi catalyzed C(sp3)—H borylation of alkanes

图式12. Ir-NSiN金属络合物催化的C(sp2)—H硅基化反应

Scheme 12. Ir-NSiN complex catalyzed C(sp2)—H silylation reaction

图式13. Ru-xantsil 金属络合物催化的芳基炔烃的C(sp2)—H硅基化及氢化反应

Scheme 13. Ru-xantsil complexes catalyzed C(sp2)—H silylation and hydrogenation of arylalkynes

图式14. Ru-xantsil 金属络合物催化的芳基炔烃的C(sp2)—H硅基化及硅氢化反应

Scheme 14. Ru-xantsil complexes catalyzed C(sp2)—H silylation and hydrosilylation of arylalkynes

图式15. 手性硅基配体介导的分子间不对称C(sp2)—H硅基化反应

Scheme 15. Chiral silyl ligands mediated intermolecular enantioselective C(sp2)—H silylation

图式16. 手性硅基配体介导的分子间不对称C(sp2)—H硅基化反应的机理研究

Scheme 16. Proposed mechanism for the chiral silyl ligand mediated enantioselective C(sp2)—H silylation

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