Dimethyl Sulfoxide/Potassium Hydroxide: A Superbase for the Transition Metal‐Free Preparation of Cross‐Coupling Products

Yu, Yuan; Thomé, Isabelle; Kim, Seok Hwan; Chen, Duanteng; Beyer, Astrid; Bonnamour, Julien; Zuidema, Erik; Chang, Sukbok; Bolm, Carsten

doi:10.1002/adsc.201000575

Cited by 152 publications

(63 citation statements)

References 91 publications

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“…Electrophilic coupling partners have only stable functional groups such as methyl, methoxy, fluoride, amino, nitro, and hydroxy. 15 For control experiment, reaction of chlorobenzaldehyde and ethyl 4-chlorobenzoate with benzenethiol using KOH/DMSO at 130°C was carried out, providing the corresponding sulfide in low yield.…”

Section: A12mentioning

confidence: 99%

Palladium-catalyzed Carbon–Sulfur Cross-coupling Reactions of Aryl Chlorides with Indium Tris(organothiolates)

MoJuntae¹,

EomDahan²,

Hong³

et al. 2011

Chemistry Letters

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Pd-Catalyzed carbonsulfur cross-coupling reactions of aryl chlorides with indium tris(organothiolates) were developed. Aryl chlorides reacted with indium tris(organothiolates) (0.35 equiv) in the presence of 4 mol % of Pd(OAc) 2 , 4.2 mol % of Xantphos, and Cs 2 CO 3 as an additive, producing arylaryl and arylalkyl sulfides in good to excellent yields.Cross-coupling reaction is one of the most straightforward and versatile methods in organic synthesis.1 Advances in transition-metal catalysis make it possible to couple an electrophilic coupling partner with a nucleophilic coupling partner with high efficiencies and broad substrate scopes. Especially, the transition-metal-catalyzed carbonsulfur cross-coupling reaction is one of the fundamental processes in organic synthesis because the sulfide group is widely used in pharmaceuticals, functional materials, and synthesis of natural products.2 Over the last decades, transition metals, such as Pd, 3 Ni, 4 Cu, 5 and Fe, 6 have been applied in carbonsulfur cross-coupling reactions, leading to the effective synthesis of sulfides. In continuation of our studies directed toward the development of efficient indiummediated organic reactions, we reported Pd-catalyzed crosscoupling reactions using allylindiums, 7 allenylindiums, 8 1,3-butadien-2-ylindiums, 9 tetra(organo)indates, 10 and vinylindiums 11 with a wide range of functional group tolerance.10a,12Moreover, we developed recently indium tris(organothiolate) as a nucleophilic cross-coupling partner in Pd-catalyzed CS crosscoupling reactions using aryl bromide and iodide as an electrophile. 13 There is great interest in developing carbonsulfur crosscoupling reactions that use aryl chlorides because they are readily available, inexpensive, and environmentally strategic reagents.3d,14 Herein, Pd-catalyzed carbonsulfur cross-coupling reactions of aryl chlorides with indium tris(organothiolates) are described (Scheme 1).Although optimum conditions obtained from Pd-catalyzed CS cross-coupling reaction of aryl bromide with indium tris(phenylthiolate) applied to p-chloronitrobenzene (1a), 4-nitrophenyl phenyl sulfide (3a) was produced in 30% yield. 13These results led us to investigate intensively Pd-catalyzed CS cross-coupling reaction of aryl chloride with indium tris(organothiolate). First, several additives and ligands were examined and the results are summarized in Table 1. Use of sodium iodide gave similar results to DIPEA (Entry 2). Lithium iodide afforded 3a in moderate yield (Entries 3 and 4), whereas lithium bromide (2 equiv) increased to 75% yield (Entry 6). Next, a wide range of ligand in the presence of lithium bromide (2 equiv) as an additive was examined (Entries 711). Although Cy 3 P, (p-MeO-C 6 H 4 ) 3 P, and (p-CF 3 -C 6 H 4 ) 3 P did not give 3a, (Biph)PCy 2 and DPEDIPphos produced 3a in 78% and 81% yields, respectively (Entries 7 and 9). Coupling reaction did not proceed with Na 2 CO 3 as an additive (Entry 12). However, use of Cs 2 CO 3 (2 equiv) with 4 mol % Pd(OAc) 2 and 4.2 mol % Xantphos in DMF (110°C,...

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Section: A12mentioning

confidence: 99%

Palladium-catalyzed Carbon–Sulfur Cross-coupling Reactions of Aryl Chlorides with Indium Tris(organothiolates)

MoJuntae¹,

EomDahan²,

Hong³

et al. 2011

Chemistry Letters

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“…Strong bases, such as isopropylmagnesium chloride or hexyllithium, are required. Other reaction conditions, such as sulfur in KOH/ DMSO (Yuan et al, 2010), K 2 CO 3 /MeOH (Ansell et al, 1970) or Et 3 N/pyridine (Becker et al, 1973), did not yield the desired product.…”

Section: Structure Descriptionmentioning

confidence: 97%

1-Vinyl-4-imidazoline-2-thione

et al. 2017

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“…However, we never experienced selectivity problems, even at elevated temperatures. [18] Concerning the possibility of free-radical S N Ar mechanisms (S RN 1), radical scavengers TEMPO, galvinoxyl and acrylonitrile failed to inhibit the reactions shown in Table 2, suggesting that radicals are not involved.…”

mentioning

confidence: 99%

“…It was observed that an elevated temperature (145 °C) is necessary to furnish the desired diaryl ether 11 in moderate to excellent yields (Table 2, entries [16][17][18]. When the reactions were repeated at 120 °C with the 3 aryl halides, the best conversion was obtained in the case of 4-bromoacetophenone, while 4-iodo and 4-chloroacetophenone gave modest results (Table 2, entries 16'-18').…”

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confidence: 99%

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On the Frontier Between Nucleophilic Aromatic Substitution and Catalysis

Drapeau¹,

Ollevier²,

Taillefer³

2014

Chemistry A European J

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A study on the arylation of heteroatom nucleophiles by using activated haloarenes, with or without metal catalysts, is reported. A discussion concerning the involvement of traces of metals is presented, supported by an unexpected ''ligand'' effect in the absence of added metal catalysts. We believe that the frontier between nucleophilic aromatic substitution and catalysis will likely prove to be much harder to delimit than is generally thought.

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Dimethyl Sulfoxide/Potassium Hydroxide: A Superbase for the Transition Metal‐Free Preparation of Cross‐Coupling Products

Abstract: Potassium hydroxide (KOH) in dimethyl sulfoxide (DMSO) forms a superbasic medium that allows one to access cross-coupling products from reactions between aryl halides with various sulfur-, oxygen-and nitrogen-based nucleophiles under transition metal-free conditions.

Cited by 152 publications

References 91 publications

Palladium-catalyzed Carbon–Sulfur Cross-coupling Reactions of Aryl Chlorides with Indium Tris(organothiolates)

Palladium-catalyzed Carbon–Sulfur Cross-coupling Reactions of Aryl Chlorides with Indium Tris(organothiolates)

1-Vinyl-4-imidazoline-2-thione

On the Frontier Between Nucleophilic Aromatic Substitution and Catalysis

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