Lewis acid-catalyzed synthesis of silafluorene derivatives from biphenyls and dihydrosilanes <i>via</i> a double sila-Friedel–Crafts reaction

Dong, Yafang; Takata, Yuta; Yoshigoe, Yusuke; Sekine, Kohei; Kuninobu, Yoichiro

doi:10.1039/c9cc07692a

Cited by 19 publications

(11 citation statements)

References 41 publications

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“…345,346,374 By combining Ingleson's and Hou's protocol (see Schemes 55 and 58), Kuninobu and co-workers accomplished the synthesis of dibenzosiloles from amino-substituted biphenyl compounds and dihydrosilanes via a double sila-Friedel−Crafts reaction (not shown). 379 As already noted by Ingleson and co-workers, 369 the B(C 6 F 5 ) 3 -catalyzed dehydrogenative silylation of indoles is accompanied by hydrogenation to the corresponding indoline, which can undergo further side reactions (e.g., C5-silylation). Zhang and co-workers turned this unselective process into a highyielding convergent method for the exclusive C3-silylation of indoles by using Ph 3 SiH (or MePh 2 SiH) and elevated reaction temperatures of 120 °C (158 → 159, Scheme 59).…”

Section: Sila-friedel−crafts Reactionsmentioning

confidence: 76%

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

et al. 2021

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The history of silyl cations has all the makings of a drama but with a happy ending. Being considered reactive intermediates impossible to isolate in the condensed phase for decades, their actual characterization in solution and later in solid state did only fuel the discussion about their existence and initially created a lot of controversy. This perception has completely changed today, and silyl cations and their donor-stabilized congeners are now widely accepted compounds with promising use in synthetic chemistry. This review provides a comprehensive summary of the fundamental facts and principles of the chemistry of silyl cations, including reliable ways of their preparation as well as their physical and chemical properties. The striking features of silyl cations are their enormous electrophilicity and as such reactivity as super Lewis acids as well as fluorophilicity. Known applications rely on silyl cations as reactants, stoichiometric reagents, and promoters where the reaction success is based on their steady regeneration over the course of the reaction. Silyl cations can even be discrete catalysts, thereby opening the next chapter of their way into the toolbox of synthetic methodology.

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Section: Sila-friedel−crafts Reactionsmentioning

confidence: 76%

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

et al. 2021

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“…This newly developed protocol allows the rapid synthesis of not only dibenzophospholes but also six- and seven-membered phosphacycles and largely π-extended P-containing heteroacene derivatives. A related reaction of more reactive 1,3-dienes with dichlorophosphines RPCl 2 to provide the monocyclic phospholes is known as the McCormack reaction, but the extension to the biaryl system remains largely elusive …”

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confidence: 99%

Direct Synthesis of Dibenzophospholes from Biaryls by Double C–P Bond Formation via Phosphenium Dication Equivalents

2020

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We have developed a new strategy for the generation of phosphenium dication equivalents from readily available phosphinic acids and Tf 2 O. The in situ-generated dication equivalents can be readily coupled with simple (hetero)biaryls to form the corresponding dibenzophospholes directly. This protocol can also be applied to the concise synthesis of six-and seven-membered phosphacycles as well as the largely π-extended heteroacene derivatives, which are of great interest in the field of organic functional materials.

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“…The classical method of preparing aryl silanes generally involves the use of halogenated arenes, via halogen–metal exchange, followed by the addition of silicon electrophiles, such as halosilanes . Catalytic Friedel–Crafts C–H silylation to electron-rich arenes or heteroarenes provided another protocol . Meanwhile, transition-metal-catalyzed cross dehydrogenative coupling (CDC) of C–H with Si–H bond also displayed an efficient approach for this purpose .…”

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confidence: 99%

Selective C-5 Oxidative Radical Silylation of Imidazopyridines Promoted by Lewis Acid

Shu

Liu

et al. 2020

Org. Lett.

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An oxidative cross dehydrogenative coupling of imidazopyridines with silanes was developed using di-tert-butyl peroxide as the oxidant. The coordination effect of Lewis acid was the dominant factor controlling the regioselective addition of silyl radical to imidazopyridines, and the corresponding C-5 silylated imidazo[1,2-a]pyridines were obtained in moderate to high yields with a broad substrate scope.

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Lewis acid-catalyzed synthesis of silafluorene derivatives from biphenyls and dihydrosilanes via a double sila-Friedel–Crafts reaction

Abstract: The synthesis of silafluorene derivatives from aminobiphenyl compounds and dihydrosilanes via a double sila-Friedel–Crafts reaction using a borane catalyst has been achieved.

Cited by 19 publications

References 41 publications

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Direct Synthesis of Dibenzophospholes from Biaryls by Double C–P Bond Formation via Phosphenium Dication Equivalents

Selective C-5 Oxidative Radical Silylation of Imidazopyridines Promoted by Lewis Acid

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