X-Type Silyl Ligands Mediated C—H Functionalization Reactions

doi:10.6023/cjoc202406014

Abstract

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

Cite this article

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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Fig. & Tab. 16

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

Scheme 2. Properties of silyl-metal complexes

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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X类型硅基配体介导的碳氢官能化反应