A New Transformation of Silanols. Palladium-Catalyzed Cross-Coupling with Organic Halides in the Presence of Silver(I) Oxide

Hirabayashi, Kazunori; Kawashima, Jun; Nishihara, Yasushi; Mori, Atsunori; Hiyama, Tamejiro

doi:10.1021/ol990614c

Cited by 169 publications

(55 citation statements)

References 10 publications

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“…C À C bond formation by Hiyama cross-coupling with an iodoarene using silver(I) oxide as an activator afforded para-terphenyl derivative 5. [16,17] Modification of the allyl group under Heck arylation conditions in the presence of TBAF afforded desilylprotonated styrene derivative 6. [a] Allylsilane (10 equiv) was used.…”

Section: Single C à F Bond Cleavage Of Trifluoromethylarenes With An mentioning

confidence: 99%

Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho‐Silyl Group

et al. 2016

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The transformation of a single C-F bond of trifluoromethylarenes bearing a hydrosilyl group at the ortho position was achieved. The activation of the hydrosilyl group with a trityl cation in the presence of nucleophiles allowed for selective C-F bond functionalization, for example, by allylation, carboxylation, or chlorination. Further derivatization of the resulting fluorosilylarenes afforded various aromatic difluoromethylene compounds.

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Section: Single C à F Bond Cleavage Of Trifluoromethylarenes With An mentioning

confidence: 99%

Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho‐Silyl Group

et al. 2016

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“…[20] Later, arylsilanols, [21] trialkoxy(aryl)-silanes, [22] poly(phenylsiloxane)s, [23] aryl(halo)silacyclobutanes, [24] arylsilatranes, [25] and triethylammonium arylbis(catecholato)silicates [26] were used for the crosscoupling with aryl halides and triflates.…”

Section: Introductionmentioning

confidence: 99%

Cross‐Coupling of Triallyl(aryl)silanes with Aryl Bromides and Chlorides: An Alternative Convenient Biaryl Synthesis

et al. 2004

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Cross-coupling of a diverse range of aryl bromides with triallyl(aryl)silanes is effective in the presence of PdCl 2 /PCy 3 and tetrabutylammonium fluoride (TBAF) in DMSO-H 2 O to give various biaryls in good yields. It is worthwhile to note that the all-carbon-substituted arylsilanes, stable towards moisture, acid, and base and easily accessible, serve as a highly practical alternative to their aryl(halo)silane counterparts. A catalyst system consisting of [(h 3 -C 3 H 5 )PdCl] 2 and 2-[2,4,6-(i-Pr) 3 C 6 H 2 ]-C 6 H 4 PCy 2 and use of TBAF · 3 H 2 O in THF-H 2 O are effective especially for the cross-coupling with aryl chlorides. Both of the catalyst systems tolerate a broad spectrum of common functional groups. The high efficiency of reactions is presumably due to the ready cleavage of the allyl groups upon treatment with TBAF · 3 H 2 O and an appropriate amount of water. Diallyl(diphenyl)silane also cross-couples with various aryl bromides and chlorides in good yields, whereas allyl(triphenyl)silane gives the cross-coupled products in only moderate yields. Through sequential cross-coupling of bromochlorobenzenes with different arylsilanes, a range of unsymmetrical terphenyls are accessible in good overall yields.

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“…In this study, the best activator was found to be silver (I) oxide, which promoted the coupling of aryl silanol 6 to a variety of aryl iodides (Chart 2). 17,18) The common silicon coupling promoter, tetrabutylammonium fluoride (TBAF), was ineffective in this method. Alkenylsilanols were also employed with similar success.…”

Section: Organosilanol Cross-couplingmentioning

confidence: 99%

Cross-Coupling Reactions of Organosilicon Compounds: New Concepts and Recent Advances.

Denmark

Sweis

2002

CHEMICAL & PHARMACEUTICAL BULLETIN

114

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Palladium-catalyzed cross-coupling reactions occupy a unique status among methods for the construction of carboncarbon bonds. The well-established Stille-Migita-Kosugi coupling of organostannanes [1][2][3] and the Suzuki-Miyaura coupling of organoboron compounds 4,5) are two reactions that, until recently, have been the "gold-standard" among various palladium-catalyzed coupling reactions. Their wide use and extraordinary synthetic utility have provided the impetus to develop newer and more effective variants (Fig. 1). More recently organosilanes have also been shown to be competent coupling partners in those reactions that employ shelf-stable reagents. The early work of Hiyama demonstrated that in the presence of a nucleophilic promoter, fluorosilanes could undergo a variety of cross-coupling reactions whose scope rivaled that of organotin and organoboron cross-couplings. [6][7][8] Since these reports, many variants of organosilicon crosscoupling have been developed that extend beyond the use of fluorosilanes and that possess many attractive features which now elevate this method to be a viable alternative to other types of cross-coupling. This report will outline recent advances in the development of organosilicon cross-coupling reactions and provide an overview of scope and applicability of this new technology.Organosilanes were previously thought to be too unreactive to be effective cross-coupling partners. The small electronegativity difference between silicon and carbon resulted in a relatively weak nucleophilic reagent for the cross-coupling. The use of fluorosilanes was therefore a significant breakthrough, demonstrating that in the presence of a nucleophilic promoter, these compounds could access a pentacoordinate "ate" species, which was postulated to undergo the coupling reaction due to its enhanced polarization at the carbon-silicon bond. Because silicon-based compounds are generally non-toxic, have low molecular weight, and are easily incorporated into molecules by a variety of methods, the potential for developing other silicon-based cross-coupling systems superior to methods previously employed was recognized.One of the first successful alternatives to fluorosilanes in organosilicon cross-coupling was achieved through the use of siletanes. Predicated on the necessity to generate a pentacoordinate silicon for the coupling process, it was hypothesized that the use of a siletane should enable generation of the pentacoordinate silicate more readily in the presence of a nucleophile due to the enhanced Lewis acidity of the silicon. This property is a manifestation of "strain release Lewis acidity" which has its origins in the difference in coordination geometry between four coordinate (tetrahedral) and five coordinate (trigonal bipyramidal) silicon species (Fig. 2). Therefore, the angle strain in a four coordinate siletane (79°vs. 109°) is partially relieved upon binding a fifth ligand to produce a trigonal bipyramidal species (79°vs. 90°) in which the siletane bridges an apical and basal position. 9,10)...

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A New Transformation of Silanols. Palladium-Catalyzed Cross-Coupling with Organic Halides in the Presence of Silver(I) Oxide

Abstract: The reactions of aryl- and alkenylsilanols with organic halides are found to proceed in a catalyst system of 5 mol % of Pd(PPh3)4 and Ag2O (1 equiv) to give the corresponding coupling products in up to 84% yield.

Cited by 169 publications

References 10 publications

Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho‐Silyl Group

Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho‐Silyl Group

Cross‐Coupling of Triallyl(aryl)silanes with Aryl Bromides and Chlorides: An Alternative Convenient Biaryl Synthesis

Cross-Coupling Reactions of Organosilicon Compounds: New Concepts and Recent Advances.

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