Palladium-Catalyzed Silylation of Aryl Bromides Leading to Functionalized Aryldimethylsilanols

Denmark, Scott E.; Kallemeyn, Jeffrey M.

doi:10.1021/ol035288m

Cited by 110 publications

(44 citation statements)

References 15 publications

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“…Another method is the catalytic conversion of C-H bonds to C-Si bonds in the presence of transition-metal complexes [5,6]. Different research groups separately reported on the transition-metal-catalyzed coupling reaction of aryl halides with trialkoxysilanes [7][8][9][10][11]. Although, trialkylsilanes (e.g., Et 3 SiH) have not been found suitable silylating agent in some catalytic systems [12], recently, their use to attain the silylation of aryl halides under Pd and Pt catalysis have been reported [13,14].…”

Section: Introductionmentioning

confidence: 99%

Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Iranpoor

Firouzabadi

Azadi

2010

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Iranpoor

Firouzabadi

Azadi

2010

Journal of Organometallic Chemistry

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“…The silyl group must withstand the conditions of the heteroannulation and then undergo hydrolysis to the silanol with out protodesilylation under mild conditions 33. Thus, 1-heptyne was lithiated and the lithioalkyne trapped with dimethyl chlorosilane to afford silyl hydride 9 in 70% yield (Scheme 2, eq.…”

Section: Resultsmentioning

confidence: 99%

“…First, the development of an alkynyl silyl ether that is stable under the heteroannulation conditions, but easily cleaved without protodesilylation posed a difficult challenge. This challenge is particularly important in light of studies that demonstrated that silyl ethers can be cleaved under basic conditions33 and premature release of the silanol could lead to undesired side products. Furthermore, the cross-coupling of (2-indolyl)silanols bearing a substituent at the C(3) position has not been studied.…”

Section: Introductionmentioning

confidence: 99%

Preparation of 2,3-disubstituted indoles by sequential Larock heteroannulation and silicon-based cross-coupling reactions

Denmark

Baird

2009

Tetrahedron

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A simple and convergent synthesis of 2,3-disubstituted indoles has been developed using a sequential Larock indole synthesis and silicon-based, cross-coupling reaction. Substituted 2-iodoanilines reacted with an alkynyldimethylsilyl tert-butyl ether to afford indole-2-silanols under the Larock heteroannulation conditions after hydrolysis. The corresponding sodium 2-indolylsilanolate salts successfully engaged in cross-coupling with aryl bromides and chlorides to afford multi-substituted indoles. The development of an alkynyldimethylsilyl tert-butyl ether as a masked silanol equivalent enabled a smooth heteroannulation process and the identification of a suitable catalyst/ligand combination provided for a facile cross-coupling reaction.

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“…3). 25 For effective reaction with aryl bromides, a bulky electron-rich phosphine (JohnPhos) 26 is required. The pH of the workup is critical to suppress formation of the disiloxane.…”

Section: Silanolsmentioning

confidence: 99%

Why You Really Should Consider Using Palladium-Catalyzed Cross-Coupling of Silanols and Silanolates

Denmark

Ambrosi

2015

Org. Process Res. Dev.

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157

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The transition metal-catalyzed cross-coupling of organometallic nucleophiles derived from tin, boron, and zinc with organic electrophiles enjoys a preeminent status among modern synthetic methods for the formation of carbon-carbon bonds. In recent years, organosilanes have emerged as viable alternatives to the conventional reagents, with the added benefits of low cost, low toxicity and high chemical stability. However, silicon-based cross-coupling reactions often require heating in the presence of a fluoride source, which has significantly hampered their widespread acceptance. To address the “fluoride problem”, a new paradigm for palladium-catalyzed, silicon-based cross-coupling reactions has been developed that employs a heretofore underutilized class of silicon reagents, the organosilanols. The use of organosilanols, either in the presence of Brønsted bases or as their silanolate salts, represents an operationally simple and mild alternative to the fluoride-based activation method. Organosilanols are readily available by many well-established methods for introducing carbon-silicon bonds onto alkenes, alkynes, arenes and heteroarenes. Moreover, several different protocols for the generation of alkali metal salts of, vinyl-, alkenyl-, alkynyl-, aryl-, and heteroarylsilanolates have been developed and the advantages of each of these methods have been demonstrated for a number of different coupling classes. This review will describe the development and implementation of cross-coupling reactions of organosilanols and their conjugate bases, silanolates, with a wide variety of substrate classes. In addition, application of these transformations in the total synthesis of complex natural products will also be highlighted. Finally, the unique advantages of organosilicon coupling strategies vis a vis organoboron reagents are discussed.

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Palladium-Catalyzed Silylation of Aryl Bromides Leading to Functionalized Aryldimethylsilanols

Cited by 110 publications

References 15 publications

Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Preparation of 2,3-disubstituted indoles by sequential Larock heteroannulation and silicon-based cross-coupling reactions

Why You Really Should Consider Using Palladium-Catalyzed Cross-Coupling of Silanols and Silanolates

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