Efficient and C2-selective arylation of indoles, benzofurans, and benzothiophenes with iodobenzenes in water at room temperature

Xu, Zhongmiao; Xu, Yulong; Lu, Huiqing; Yang, Ting; Lin, Xichen; Shao, Liming; Ren, Feng

doi:10.1016/j.tet.2015.03.051

Cited by 45 publications

(42 citation statements)

References 41 publications

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“…Related studies examining C‐2 arylations of indoles, benzofurans, and iodobenzenes have found that micelles derived from Tween 80 in water lead to net C−H activation/coupling at room temperature (25 °C) . Again, CF 3 CO 2 Ag was an important additive in this reaction, with 1.5 equivalents being used in addition to five mole percent of the Pd catalyst, all designed to accelerate these reactions that reached full conversion in one hour.…”

Section: Spotlight On Pd Catalysismentioning

confidence: 98%

“…Related studies examiningC -2 arylations of indoles, benzofurans, and iodobenzenes have found that micelles derived from Tween 80 in water lead to net CÀHa ctivation/coupling at room temperature (25 8C). [32] Again, CF 3 CO 2 Ag was an important additive in this reaction, with 1.5 equivalents being used in addition to five mole percent of the Pd catalyst, all designed to accelerate these reactions that reached full conversion in one hour.I nt he indole series, both Nmethyl and the free NH-indole could be arylated selectively at the C-2 site (Scheme 14, line 1). Likewise, benzofurans underwent similarC -2 arylations, albeit requiring far longerr eactiont imes (Scheme 14, line 2) along with the presence of added TFA( 2equiv).…”

Section: Càha Rylationmentioning

confidence: 99%

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The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

Lipshutz

Ghorai²,

Cortes‐Clerget

2018

Chemistry A European J

282

182

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Recent developments over the past few years in aqueous micellar catalysis are discussed. Applications to problems in synthesis are highlighted, enabled by the use of surfactants that self-aggregate in water into micelles as nanoreactors. These include amphiphiles that have been available for some time, as well as those that have been newly designed. Reactions catalyzed by transition metals, including Pd, Cu, Rh, and Au, are of particular focus.

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Section: Spotlight On Pd Catalysismentioning

confidence: 98%

Section: Càha Rylationmentioning

confidence: 99%

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

Lipshutz

Ghorai²,

Cortes‐Clerget

2018

Chemistry A European J

282

182

View full text Add to dashboard Cite

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“…Herein we report studies leading to the discovery of a novel Ag(I)–C–H activation-based methodology that overcomes the aforementioned limitations and affords the first near-room-temperature C2-arylation of benzo[ b ]thiophenes. 8 This new methodology offers wide functional group tolerance, operates at near room temperature, and requires only 0.4 mol % Pd-catalyst loading.…”

Section: Introductionmentioning

confidence: 99%

Ag(I)–C–H Activation Enables Near-Room-Temperature Direct α-Arylation of Benzo[b]thiophenes

et al. 2018

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The first example of near-room-temperature α-arylation of benzo[ b]thiophenes is reported. The discovery rests on the observation of a switch in α-/β-regioselectivity at different loadings of Pd(dba)·CHCl in the coupling between benzo[ b]thiophene and 4-iodotoluene. We show that this unprecedented regioselectivity switch is driven by a Ag(I)-mediated C-H activation at the α-C-H position, which becomes the dominant mode of reactivity at low concentrations of Pd. Competition experiments, kinetic studies, KIE, and D/H scrambling experiments have been carried out supporting this mechanism.

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“…In 1990, Ohta et al reported that the C–H arylation of benzofuran using arylbromides in the presence of catalytic Pd(PPh 3 ) 4 and excess amount of potassium acetate gave 2-phenylbenzofuran in 23% yield [ 15 ]. Since then, the reaction conditions using aryl halides have been improved in order to obtain 2-arylbenzofurans more efficiently [ 16 , 17 , 18 , 19 , 20 ]. Reactions using other aryl donors to replaces the aryl halides have also been developed ( Scheme 1 ).…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed C–H Arylation of Benzofurans with Triarylantimony Difluorides for the Synthesis of 2-Arylbenzofurans

Kitamura¹,

Murata²,

Iwai³

et al. 2020

Molecules

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Pd-catalyzed regioselective C–H arylation is a useful tool for the chemical modification of aromatic heterocycles and 2-arylbenzofuran derivatives are of interest as biologically active substances. Herein, the reaction of triarylantimony difluorides with benzofurans under aerobic conditions in 1,2-DCE, using 5 mol% Pd (OAc)2 and 2 eq. of CuCl2 at 80 °C, produced a variety of 2-arylbenzofurans in moderate-to-high yields. The reaction is sensitive to the electronic nature of the substituents on the benzene ring of the triarylantimony difluorides: an electron-donating group showed higher reactivity than an electron-withdrawing group. Single crystal X-ray analysis of tri(p-methylphenyl) antimony difluoride revealed that the central antimony atom exhibits trigonal bipyramidal geometry.

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Efficient and C2-selective arylation of indoles, benzofurans, and benzothiophenes with iodobenzenes in water at room temperature

Cited by 45 publications

References 41 publications

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry “in Water”

Ag(I)–C–H Activation Enables Near-Room-Temperature Direct α-Arylation of Benzo[b]thiophenes

Palladium-Catalyzed C–H Arylation of Benzofurans with Triarylantimony Difluorides for the Synthesis of 2-Arylbenzofurans

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