Research Progress in Transition-Metal-Free C—Si Bond Formation

doi:10.6023/cjoc202307017

Abstract

Organosilicons are widely used in many chemistry related fields. Given its important role, the chemical syntheses of organosilicon compounds have received considerable attention. Due to outstanding advantages in cost and environmental friendliness, transition-metal-free C—Si bond formation has been widely studied in the past decades and has been emerged as an important alternative to transition-metal-catalyzed C—Si cross-coupling. In this review, the recent developed methods of carbon-silicon bond formation under transition-metal-free conditions are summarized. The discussion is organized according to catalysts (acid catalysis, base catalysis, and radical initiation) and the types of C—Si bonds that formed. In addition, mechanistic discussions of representative reactions and a prospect for future development in this field are also briefly included.

Key words: transition-metal-free, C—Si bond formation, organosilicons, green chemistry

Cite this article

Qiyang Li, Haiyan Zhang, Wenbo Liu. Research Progress in Transition-Metal-Free C—Si Bond Formation[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3470-3490.

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Fig. & Tab. 39

Scheme 1. General mechanism of Lewis acid-catalyzed reductive silylation reaction

Scheme 2. β-Silylative reduction of quinolines

Scheme 3. Selective silylative reduction of pyridines

Scheme 4. Ring-opening and closing cascades of furans

Scheme 5. Silylative reductive of conjugated nitriles and unsaturated imines

Scheme 6. Olefin hydrosilylation mediated by phosphorus(III) Lewis acid

Scheme 7. Silylation of the benzyl-substituted vinylcyclopropanes

Scheme 8. Consecutive silylation of tertiary amines

Scheme 9. C—H bond silylation of aromatic amine

Scheme 10. Convergent disproportionation reaction of indoles

Scheme 11. Mechanism of convergent disproportionation reaction of indoles

Scheme 12. C—H silylation of indoles catalyzed by Al(C6F5)3

Scheme 13. Cascade silylation of piperidines

Scheme 14. C—H silylation of terminal alkynes

Scheme 15. Deprotonative C—H silylation of (hetero-)arenes

Scheme 16. tBuOK-catalyzed dehydrogenative silylation of heteroaromatics

Scheme 17. Mechanism of dehydrogenative silylation of heteroaromatics

Scheme 18. Site-selective C(sp2)—H silylation of azines

Scheme 19. Alkali metal-hydroxide-catalyzed C(sp)—H silylation

Scheme 20. DMPU-mediated silylation of substituted phenylacetylene

Scheme 21. Application of silyldiazenes in silylation of C(sp2)—H bond

Scheme 22. tBuONa-mediated gem-silylborylation of α-oxyboronates

Scheme 23. Base-mediated borylsilylation/silylation of ammonium salts

Scheme 24. Silyldefluorination of fluorohydrocarbon by concerted substitution

Scheme 25. Silyldefluorination of fluoroarenes by concerted substitutioni

Scheme 26. KOtBu-catalyzed 1,2-silaboration of N-heteroarenes

Scheme 27. Silylative aromatization of p-quinone methides

Scheme 28. Ring-opening silylation of indoles and benzofurans

Scheme 29. CsF-mediated hydrotrimethylsilylation of styrenes with anti-Markovnikov selectivity

Scheme 30. Radical silylation of electron-deficient N-hetero- arenes

Scheme 31. Dehydrogenative silylation of enamides

Scheme 32. Synthesis of 9-silafluorenes via base-promoted homolytic aromatic substitution (BHAS)

Scheme 33. Radical-mediated synthesis of alkenyl silanes by C—S bond cleavage of arylalkenyl sulfides

Scheme 34. Oxidative radical reaction access to Si-containing heterocycles

Scheme 35. Radical-initiated cascade addition/cyclization

Scheme 36. Regioselective silylations through Ca-promoted reductive C—O bond cleavage

Scheme 37. Hydrogen atom transfer(HAT) to vinylarenes for hydrosilylation

Scheme 38. Calcium-catalyzed dehydrogenative silylation of (hetero-)arenes

Scheme 39. Organocalcium complex-catalyzed C—Si bond formation

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