Modular Approach to Silicon‐Bridged Biaryls: Palladium‐Catalyzed Intramolecular Coupling of 2‐(Arylsilyl)aryl Triflates

Shimizu, Masaki; Mochida, Kenji; Hiyama, Tamejiro

doi:10.1002/ange.200804146

Cited by 60 publications

(17 citation statements)

References 82 publications

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“…A variety of electron-rich azoles was directly arylated efficiently with aryl iodides, triflates, [141] and bromides as electrophiles. [142] Specifically, benzoxazoles turned out to be excellent substrates for palladium-catalyzed direct arylation, which occurred selectively at the C2-position (Scheme 70).…”

Section: Methodsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Direct Arylation of (Hetero)Arenes by CH Bond Cleavage

2009

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The area of transition-metal-catalyzed direct arylation through cleavage of C-H bonds has undergone rapid development in recent years, and is becoming an increasingly viable alternative to traditional cross-coupling reactions with organometallic reagents. In particular, palladium and ruthenium catalysts have been described that enable the direct arylation of (hetero)arenes with challenging coupling partners--including electrophilic aryl chlorides and tosylates as well as simple arenes in cross-dehydrogenative arylations. Furthermore, less expensive copper, iron, and nickel complexes were recently shown to be effective for economically attractive direct arylations.

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Section: Methodsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Direct Arylation of (Hetero)Arenes by CH Bond Cleavage

2009

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“…[7][8][9] In contrast to the classical cross-coupling methods, reactions of this type often only require easily accessible starting materials, although lower regioselectivity and double arylation are still potential risks.…”

Section: Introductionmentioning

confidence: 99%

Radical Arylation of Phenols, Phenyl Ethers, and Furans

Wetzel

Pratsch

Kolb

et al. 2010

Chemistry A European J

108

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Radical arylations of para-substituted phenols and phenyl ethers proceeded with good regioselectivity at the ortho position with respect to the hydroxy or alkoxy group. The reactions were conducted with arenediazonium salts as the aryl radical source, titanium(III) chloride as the reductant, and diluted hydrochloric acid as the solvent. Substituted biaryls were obtained from hydroxy- and alkoxy-substituted benzylamines, phenethylamines, and aromatic amino acids. The methodology described offers a fast, efficient, and cost-effective new access to diversely functionalized biphenyl alcohols and ethers. Free phenolic hydroxy groups, aromatic and aliphatic amines, as well as amino acid substructures, are well tolerated. Two examples for the applicability of the methodology are the partial synthesis of a beta-secretase inhibitor and the synthesis of a calcium-channel modulator.

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“…The residue was purified by column chromatography on silica gel to give 1-8. Characterization data of 1-5 and 8 as well as their precursors is available in the supporting information of the literature we reported [47].…”

Section: Synthesis Of Heteroaromatic Ring-fused (Di)benzosiloles 1-7 mentioning

confidence: 98%

“…We recently developed palladium-catalyzed intramolecular coupling of 2-(arylsilyl)aryl triflates as a new synthetic route to silicon-bridged biaryls (eq. (1)) [47]. The modular approach allowed us to conveniently synthesize not only functionalized dibenzosiloles but also benzosiloles fused to a heteroaromatic ring.…”

Section: Introductionmentioning

confidence: 99%

Photophysical properties of heteroaromatic ring-fused (di)benzosiloles

et al. 2011

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Benzosiloles fused to heterocycles such as thiophene, benzothiophene, and benzofuran, and indole-and benzosilole-fused dibenzosiloles were prepared by palladium-catalyzed intramolecular coupling of the corresponding 2-(arylsilyl)aryl triflates in good to high yields. Molecular and crystal structures of 5,7-dihydro-5,5,7,7-tetrakis(1-methylethyl)bis[1]benzosilolo-[2,3-b:3', 2'-d]thiophene, 6-methyl-12,12-diisopropyl-12H-indololo[3,2-b][1]silafluorene, and 5,5,11,11-tetraisopropyl-5,11H-benzosilolo[3,2-c]silafluorene were determined by X-ray diffraction analysis. The UV absorption spectra of the (di)benzosilole derivatives in cyclohexane red-shifted when compared to 1,1-diisopropyldibenzosilole, indicating that replacing a benzene ring of dibenzosilole by the heterocycles as well as fusion of indole and benzosilole moieties onto dibenzosilole narrowed the HOMO-LUMO gaps of the -conjugation system. The thiophene-fused benzosiloles were faintly fluorescent in solution and in the solid state, whereas the dibenzosiloles exhibited luminescence with moderate and high quantum yields in cyclohexane and in microcrystals, respectively. In other words, aggregation-induced emission was observed for the dibenzosiloles. Notably,5,5,11,silafluorene in microcrystals exhibited violet fluorescence ( max = 396 nm) with a quantum yield of 0.70. Density functional theory (DFT) calculations of the prepared (di)benzosiloles were also performed. absorption, benzosilole, fluorescence, silicon, solid-state emission

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Modular Approach to Silicon‐Bridged Biaryls: Palladium‐Catalyzed Intramolecular Coupling of 2‐(Arylsilyl)aryl Triflates

Cited by 60 publications

References 82 publications

Transition‐Metal‐Catalyzed Direct Arylation of (Hetero)Arenes by CH Bond Cleavage

Transition‐Metal‐Catalyzed Direct Arylation of (Hetero)Arenes by CH Bond Cleavage

Radical Arylation of Phenols, Phenyl Ethers, and Furans

Photophysical properties of heteroaromatic ring-fused (di)benzosiloles

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