Sila-Sonogashira Cross-Coupling Reactions of Activated Aryl Chlorides with Alkynylsilanes

Nishihara, Yasushi; Inoue, Eiji; Okada, Yoshiaki; Takagi, Kentaro

doi:10.1055/s-0028-1087345

Cited by 41 publications

(11 citation statements)

References 8 publications

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“…This mixture can be readily converted into the desired terminal alkyne by using fluoride ions. The formation of this mixture of silyl‐protected and terminal alkynes can be rationalized from the sila‐Sonogashira–Hagihara coupling reactions reported by Nishihara and co‐workers from alkynylsilanes 61–66. In our case, trimethylsilylacetylene reacted under standard Sonogashira reaction conditions or through the silyl end under sila‐Sonogashira–Hagihara conditions to provide either the trimethylsilyl (TMS)‐protected or the terminal alkyne, respectively.…”

Section: Resultsmentioning

confidence: 68%

“…The formation of this mixture of silylprotected and terminal alkynes can be rationalized from the sila-Sonogashira-Hagihara coupling reactions reported by Nishihara and co-workers from alkynylsilanes. [61][62][63][64][65][66] In our case, trimethylsilylacetylene reacted under standard Sonogashira reaction conditions or through the silyl end under sila-Sonogashira-Hagihara conditions to provide either the trimethylsilyl (TMS)-protected or the terminal alkyne, respectively. Conjugation of the terminal alkyne 26 with the glycosyl azides 27 under CuAAC conditions provided the NDPsugar analogues 28, which were deprotected to the GT inhibitor candidates 29.…”

Section: Resultsmentioning

confidence: 99%

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Design of Glycosyltransferase Inhibitors: Pyridine as a Pyrophosphate Surrogate

Wang

Cuesta-Seijo

Lafont

et al. 2013

Chemistry A European J

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A series of ten glycosyltransferase inhibitors has been designed and synthesized by using pyridine as a pyrophosphate surrogate. The series was prepared by conjugation of carbohydrate, pyridine, and nucleoside building blocks by using a combination of glycosylation, the Staudinger-Vilarrasa amide-bond formation, and azide-alkyne click chemistry. The compounds were evaluated as inhibitors of five metal-dependent galactosyltransferases. Crystallographic analyses of three inhibitors complexed in the active site of one of the enzymes confirmed that the pyridine moiety chelates the Mn(2+) ion causing a slight displacement (2 Å) from its original position. The carbohydrate head group occupies a different position than in the natural uridine diphosphate (UDP)-Gal substrate with little interaction with the enzyme.

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Section: Resultsmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Design of Glycosyltransferase Inhibitors: Pyridine as a Pyrophosphate Surrogate

Wang

Cuesta-Seijo

Lafont

et al. 2013

Chemistry A European J

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“…In this and all of the other examples reported here, excellent [31] Yangjie Wu et al 1 mol% cyclopalladated [Pd] at 110 8C for 2-chloropyridine, while with 3-chloroA C H T U N G T R E N N U N G pyridine only a 29% conversion was observed. [32] Nishihara et al used 10 mol% [Pd] at 120 8C for 2-chloropyridine conversion with a 60% yield, [33] Buchwald et al for 3-chloropyridine 2.5 mol% [Pd] at 100 8C…”

Section: Sonogashira Couplingmentioning

confidence: 99%

Sulfonated N‐Heterocyclic Carbenes for Pd‐Catalyzed Sonogashira and Suzuki–Miyaura Coupling in Aqueous Solvents

2010

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The reactions of the N,N'-diarylimidazolium and N,N'-diarylimidazolinium salts with chlorosulfonic acid result in the formation of the respective disulfonated N-heterocyclic carbene (NHC) precursors in reasonable yields (46-77%). Water-soluble palladium catalyst complexes, in situ obtained from the respective sulfonated imidazolinium salt, sodium tetrachloropalladate (Na 2 PdCl 4 ) and potassium hydroxide (KOH) in water, were successfully applied in the copper-free Sonogashira coupling reaction in isopropyl alcohol/water mixtures using 0.2 mol% catalyst loading. The preformed (disulfonatedNHC)PdClA C H T U N G T R E N N U N G (cinnamyl) complex was used in aqueous Suzuki-Miyaura reactions at 0.1 mol% catalyst loading. The coupling protocol reported here is very useful for Sonogashira reactions of N-and S-heterocyclic aryl bromides and chlorides with aryl-and alkylacetylenes.

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“…We envisaged that a combination of transition‐metal‐catalyzed silaborations44,54–57 of unsymmetrical internal alkynes could provide a straightforward synthetic route to precursors of various multisubstituted olefins. Despite our successful synthesis of a large number of unsymmetrical diarylethynes,58–64 utilization of these compounds as substrates for silaboration is easily seen to form a mixture of regioisomers because of the very similar steric and electronic nature of the two aryl groups, which limits the diversity of regio‐ and stereospecific silylborylated products (Scheme ).…”

Section: Silaboration Of An Alkynylboronatementioning

confidence: 99%

Synthesis of Multisubstituted Olefins through Regio‐ and Stereoselective Addition of Interelement Compounds Having B–Si, B–B, and Cl–S Bonds to Alkynes, and Subsequent Cross‐Couplings

Iwasaki¹,

Nishihara²

2016

The Chemical Record

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Multisubstituted olefins are fundamental motifs in organic compounds. In this account, we describe the synthesis of organic molecules bearing an olefinic moiety by the transition-metal-catalyzed regio- and stereoselective addition of a variety of interelement compounds to alkynes. Regio- and stereoselective silaboration, diborylation, and chlorothiolation have been achieved by using the transition-metal catalysts. The subsequent cross-coupling reactions of the boron-containing alkenes to install various aryl groups afforded the corresponding tri- and tetraarylated olefins. This account describes our research on the highly regio- and stereoselective synthesis of multifunctionalized olefins such as tetraarylethenes with four different aryl groups.

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Sila-Sonogashira Cross-Coupling Reactions of Activated Aryl Chlorides with Alkynylsilanes

Abstract: The palladium/copper-cocatalyzed sila-Sonogashira cross-coupling reactions of activated aryl chlorides with alkynylsilanes under strictly nonbasic conditions yield the unsymmetrical diarylethynes in moderate to good yields.

Cited by 41 publications

References 8 publications

Design of Glycosyltransferase Inhibitors: Pyridine as a Pyrophosphate Surrogate

Design of Glycosyltransferase Inhibitors: Pyridine as a Pyrophosphate Surrogate

Sulfonated N‐Heterocyclic Carbenes for Pd‐Catalyzed Sonogashira and Suzuki–Miyaura Coupling in Aqueous Solvents

Synthesis of Multisubstituted Olefins through Regio‐ and Stereoselective Addition of Interelement Compounds Having B–Si, B–B, and Cl–S Bonds to Alkynes, and Subsequent Cross‐Couplings

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