Recent Progress in the Construction of Silacycles by Transition- Metal-Catalyzed C—H Silylation

doi:10.6023/cjoc202406022

Abstract

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

Cite this article

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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Fig. & Tab. 44

Figure 1. Representative silicon-containing functional molecules

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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