Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate

Hatanaka, Yasuo; Hiyama, Tamejiro

doi:10.1021/jo00239a056

Cited by 620 publications

(301 citation statements)

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“…32 This type of transformation is made possible by C-H silylation of arenes catalyzed by a transition-metal complex, 33 t-BuOK, 34 B(C 6 F 5 ) 3 , 35 or a Brønsted acid.…”

Section: Account Syn Lett 3 Homsi Reagents From Heteroaromatics and Hmentioning

confidence: 99%

“…Therefore, we pursued optimization of the reaction conditions to achieve cross-coupling polymerization using Ar-HOMSi reagents and examined double cross-coupling reactions using stoichiometric amounts of Ar-HOMSi and dibromoarenes. As a result, 2.1 equivalents of phenyl-HOMSi turned out to doubly couple with dibromoarenes in the presence of Pd[P(o-tolyl) 3 ] 2 (2 mol%), DPPF (2.1 mol%), CuBr·SMe 2 (3.0 mol%), Cs 2 CO 3 (4.2 equiv), 3 Å MS, and THF/NMP co-solvent in high efficiency (Scheme 7). For instance, 1,4-dibromo-2,5-dihexylbenzene, 2,7-dibromo-9,9-dioctylfluorene, and 2,5-dibromothiophene were applicable to the coupling of Ph-HOMSi and gave products 8a-c in yields higher than 90%.…”

Section: Account Syn Lett 4 Cross-coupling Polymerization With Homsi mentioning

confidence: 99%

“…Hatanaka and Hiyama first discovered that structurally simple vinyl(trimethyl)silanes coupled with aryl iodides upon activation by tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF). 3 More than a decade later, Denmark disclosed that 1-alkenyl-1-methyl-silacyclobutanes underwent cross-coupling in the presence of tetrabutylammonium fluoride (TBAF) 4 and observed a ring-opening reaction of the fourmembered silacycle by water in TBAF to produce a silanol. They considered that this silanol 2c was the true active species.…”

Section: Introductionmentioning

confidence: 99%

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Recent Progress in the Cross-Coupling Reaction Using Triorganosilyl-Type Reagents

Komiyama

Minami

Hiyama

2017

Synlett

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“…32 This type of transformation is made possible by C-H silylation of arenes catalyzed by a transition-metal complex, 33 t-BuOK, 34 B(C 6 F 5 ) 3 , 35 or a Brønsted acid.…”

Section: Account Syn Lett 3 Homsi Reagents From Heteroaromatics and Hmentioning

confidence: 99%

Section: Account Syn Lett 4 Cross-coupling Polymerization With Homsi mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Recent Progress in the Cross-Coupling Reaction Using Triorganosilyl-Type Reagents

Komiyama

Minami

Hiyama

2017

Synlett

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“…Tsuji-Trostova reakcija, također je pokazala velik potencijal zbog široke primjene i relativno jednostavnih reakcijskih uvjeta. 3 Paladijem katalizirane reakcije mogu se provoditi i s različi-tim organometalnim spojevima kao što su organokositrovi (Stille), 3,8 organocinkovi (Negishi), 9 organosilicijevi (Hiyama) 10 ili organoborovi spojevi (Suzuki). 3 Osnovni razlog za veliku upotrebu paladija u sintezi je to što se stvaranjem nove veze ugljik-ugljik pruža mogućnost novih strukturnih transformacija molekule.…”

Section: Uvodunclassified

1,3-Dipolarna cikloadicija (I. dio): Dobivanje 1,2,3-triazolnih derivata u nukleozidnoj kemiji

et al. 2015

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et al.: 1,3-Dipolarna cikloadicija (I. dio): Dobivanje 1,2,3-triazolnih derivata…, (2015) 481−498 Uvod Kada je 1953. godine obznanjen model DNA s dvostrukom uzvojnicom te objašnjen princip genetskog koda i uloga nukleinskih kiselina u stanicama, ispitivanje biološke aktivnosti nukleozida i njihovih fosforiliranih derivata postalo je fundamentalno i neiscrpno područje znanstvenog interesa. Prvi radovi iz ovog područja bili su usredotočeni na transformaciju nukleobaze vezane na neki šećer ili je transformacija provedena samo na šećernoj komponenti prirodnog nukleozida. Tek 1974. godine otkrićem prvog primjenjivog antivirusnog lijeka aciklovira 1 interes se proši-rio i na spojeve u kojima se nukleobaza i šećerna komponenta značajno razlikuju od prirodnih struktura te je otkriveno da neki od njih imaju antitumorsku, antivirusnu i/ili antibakterijsku aktivnost.U potrazi za novim biološki aktivnim nukleozidnim derivatima razvijene su brojne metode njihove sinteze. Tako je posljednjih godina intenzivno razvijeno područje primjene paladijem kataliziranih reakcija adicija i supstitucija (Richard F. Heck, Ei-ichi Negishi i Akira Suzuki; Nobelova nagrada za kemiju 2010. godine). Još šezdesetih godina prošlog stoljeća otkrivena je Heckova reakcija 2,3,4 stvaranja veze ugljik-ugljik, ali je njezina primjena intenzivirana tek osamdesetih godina kada su Bergstrom i sur. objavili nekoliko radova u kojima opisuju reakcije povezivanja nukleozida s alilnim halogenidima, 5 olefinskim spojevima, 6 alkoholima i acetatima. 7 Druga metoda Pd(0)-katalizirane reakcije alkiliranja, tzv. Tsuji-Trostova reakcija, također je pokazala velik potencijal zbog široke primjene i relativno jednostavnih reakcijskih uvjeta. 3Paladijem katalizirane reakcije mogu se provoditi i s različi-tim organometalnim spojevima kao što su organokositrovi (Stille), 3,8 organocinkovi (Negishi), 9 organosilicijevi (Hiyama) 10 ili organoborovi spojevi (Suzuki). 3Osnovni razlog za veliku upotrebu paladija u sintezi je to što se stvaranjem nove veze ugljik-ugljik pruža mogućnost novih strukturnih transformacija molekule. U tablici 1 prikazane su najčešće paladijem katalizirane reakcije povezivanja primijenjene u kemiji nukleozida.Osim što su primjenom paladijem kataliziranih reakcija pripravljeni mnogi biološki aktivni derivati nukleobaza/ nukleozida, takvi spojevi mogu biti i prekursori drugih interesantnih derivata u brojnim reakcijama. U ovom radu bit će prikazane primjene različitih alkinilnih derivata nukleobaza/nukleozida (pripravljenih paladijem kataliziranim reakcijama) u 1,3-dipolarnoj cikloadicijskoj reakciji s azidima u reakcijskim uvjetima koji omogućuju dobivanje 1,2,3-triazolnih specija. Klik-kemijaPojam klik-kemije prvi su put upotrijebili Sharpless i sur. 2001. godine, 11 a nedvojbeno predstavlja jedan od najpopularnijih pristupa u suvremenoj organskoj sintezi.12 Njime su objedinili široku paletu kemijskih reakcija nastajanja veze ugljik-heteroatom u kojima se brzo i pouzdano dolazi do produkata spajanjem više manjih jedinica. Postoji ne-1,3-Dipol...

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“…[29][30][31][32][33] Here, we report the first application of the Hiyama coupling reaction to the continuous flow reaction system.…”

mentioning

confidence: 99%

Silica-Supported Palladium-Catalyzed Hiyama Cross-Coupling Reactions Using Continuous Flow System

Yang¹,

Bae

Choe

et al. 2010

Bulletin of the Korean Chemical Society

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Palladium-catalyzed C-C bond formation reactions have been intensively studied and widely used in organic synthesis. 1A variety of reaction methods have been developed utilizing the transformation methods. In particular, palladium-catalyzed biaryl cross-coupling reactions have been performed with a number of organometallics and a wide range of aryl halides. [2][3][4] In the homogeneous catalytic systems, electron-rich, bulky phosphine-and carbene-type ligands have been developed and showed high catalytic activity in the coupling reactions of the more challenging substrates such as aryl chloride, sterically demanding aryl halides and heteroaromatic substrates.5-9 Although the cross-coupling reaction has mostly been carried out in homogeneous catalytic systems, these catalysts suffer some drawbacks such difficult catalyst recovery and separation problems. To address these problems, the immobilization of Pd catalysts on inorganic solid supports [10][11][12] or organic polymers 13-15 has been studied.Recently, the continuous flow reaction technique has been used in organic transformation reactions to afford good reactivity and availability. [16][17][18][19][20] The continuous-flow microreactors have become an alternative to traditional batch reactors for scale-up due to their numerous advantages such as surface-areato-volume ratio that enhances the surface contact between different phases when the reactor's line diameter is reduced. 21,22 Furthermore, the continuous flow system has been combined with the immobilized catalyst and applied to the palladiumcatalyzed cross-coupling reactions. In the cross-coupling reactions, Suzuki, [23][24][25] Heck 26,27 and Sonogashira 28 reactions have been used in the continuous flow reaction with a variety of immobilized palladium catalysts.To the best of our knowledge, the Hiyama cross-coupling reaction has never been used in a continuous micro-flow reaction, despite the many advantages of the silyl reagent such as its stability in air stable, nontoxicity and easy availability. 29-33Here, we report the first application of the Hiyama coupling reaction to the continuous flow reaction system.Although polymer materials have also been used as solidsupported materials, we chose silica due to its advantages of mechanical and chemical strength and easily functionalization for modification. [34][35][36] A supporting material with smaller particles is known to be better than that with larger particles due to its larger surface area of catalyst. However, very small particles are not suitable as a packing material in the continuous flow system because of their plugging tendency and high-pressure drop. Therefore, we prepared two types of silica-supported palladium catalysts: large silica particles (6 ~ 12 mesh, 1.68 ~ 3.36 mm) and small silica particles (70 ~ 270 mesh, 0.053 ~ 0.21 mm). First, we attempted to introduce the diphenylphosphino bond group in the silica gel. The silica gel was reacted with ClPPh2 in the presence of pyridine in THF at room temperature for 6 h. After washing with Et...

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Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate

Cited by 620 publications

References 1 publication

Recent Progress in the Cross-Coupling Reaction Using Triorganosilyl-Type Reagents

Recent Progress in the Cross-Coupling Reaction Using Triorganosilyl-Type Reagents

1,3-Dipolarna cikloadicija (I. dio): Dobivanje 1,2,3-triazolnih derivata u nukleozidnoj kemiji

Silica-Supported Palladium-Catalyzed Hiyama Cross-Coupling Reactions Using Continuous Flow System

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Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate

Cited by 620 publications

References 1 publication

Recent Progress in the Cross-Coupling Reaction Using Triorgano­silyl-Type Reagents

Recent Progress in the Cross-Coupling Reaction Using Triorgano­silyl-Type Reagents

1,3-Dipolarna cikloadicija (I. dio): Dobivanje 1,2,3-triazolnih derivata u nukleozidnoj kemiji

Silica-Supported Palladium-Catalyzed Hiyama Cross-Coupling Reactions Using Continuous Flow System

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Product

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Recent Progress in the Cross-Coupling Reaction Using Triorganosilyl-Type Reagents

Recent Progress in the Cross-Coupling Reaction Using Triorganosilyl-Type Reagents