Direct C–H arylation of 3-methoxythiophene catalyzed by Pd. Application to a more efficient synthesis of π-alkoxy-oligothiophene derivatives

Borghese, A.; Geldhof, Geoffroy; Antoine, Luc

doi:10.1016/j.tetlet.2006.10.130

Cited by 60 publications

(28 citation statements)

References 13 publications

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“…[7] The direct arylation of 3-methoxythiophene has been explored by Borghese and co-workers. [8] With this reactant, 2-arylated thiophenes were regioselectively obtained in yields of 28-60 %. In 1998, Lemaire and co-workers reported the direct arylation of 3-formyl-, 3-cyano-, and 3-nitrothiophene with aryl iodides.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed C2 or C5 Direct Arylation of 3‐Formylthiophene Derivatives with Aryl Bromides

Dong

Doucet

2010

Eur J Org Chem

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Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed C2 or C5 Direct Arylation of 3‐Formylthiophene Derivatives with Aryl Bromides

Dong

Doucet

2010

Eur J Org Chem

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“…The method is very attractive in terms of green chemistry, because its major by-products are not metal salts but a base associated to HX, and synthesis of an organometallic derivative can be avoided. However, for C3-substituted thiophenes, arylation generally occurred at the C2-position or gave mixtures of C2- and C5-arylated products [26–33]. The introduction of blocking groups at C2-position on thiophene derivatives in order to arylate regiospecifically the C5-positions had been reported (Fig.…”

Section: Introductionmentioning

confidence: 99%

Regiocontroled Pd-catalysed C5-arylation of 3-substituted thiophene derivatives using a bromo-substituent as blocking group

Brahim

Ammar

Soulé

2016

Beilstein J. Org. Chem.

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SummaryThe use of a bromo-substituent as blocking group at the C2-position of 3-substituted thiophenes allows the regioselective introduction of aryl substituents at C5-position via Pd-catalysed direct arylation. With 1 mol % of a phosphine-free Pd catalyst, KOAc as the base and DMA as the solvent and various electron-deficient aryl bromides as aryl sources, C5-(hetero)arylated thiophenes were synthesized in moderate to high yields, without cleavage of the thienyl C–Br bond. Moreover, sequential direct thienyl C5-arylation followed by Pd-catalysed direct arylation or Suzuki coupling at the C2-position allows to prepare 2,5-di(hetero)arylated thiophenes bearing two different (hetero)aryl units in only two steps. This method provides a “green” access to arylated thiophene derivatives as it reduces the number of steps to prepare these compounds and also the formation of wastes.

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“…The direct arylation of 3-methoxythiophene has been explored by Borghese and co-workers. 13 With this reactant, the 2-arylated thiophenes were obtained regioselectively in 28-60% yields. Rhodium catalysts have also been found to promote the direct arylation at C2 of 2-methoxythiophene.…”

mentioning

confidence: 99%

“…7 On the other hand, the palladium-catalysed regiocontrolled direct arylation of 3-substituted thiophenes has attracted less attention. [8][9][10][11][12][13][14] In 2003 Sharp and co-workers have reported conditions that allow the regioselective arylation of methyl 3-thiophenecarboxylate. 8 The use of Pd(PPh 3 ) 4 in toluene gave selectively the 2-arylated thiophene; whereas Pd 2 (dba) 3 in NMP gave a mixture of 2-and 5-arylated thiophenes in a 15:51 ratio.…”

mentioning

confidence: 99%

Palladium-Catalysed C2 or C5 Direct Arylation of 3-Substituted Thiophenes with Aryl Bromides

Dong¹,

Roy²,

Roy³

et al. 2011

Synthesis

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International audienceThe Pd(OAc)2/dppb system was found to be an efficient catalyst for the direct arylation of 3-substituted thiophene derivatives. The regioselectivity of the arylation strongly depends on the thiophene substituent and also on the nature of the aryl bromide. When using 3-formyl, 3-cyano, 3-methyl, 3-hydroxymethyl or 3-bromothiophene, the 2-arylated thiophenes were obtained with 76-95% regioselectivity; whereas, the arylation of 3-formylthiophene diethylacetal or 3-acetylthiophene gave the 5-arylated thiophenes with 52-90% regioselectivity. The use of congested aryl bromides favours the arylation at C5. These reactions were performed using only 0.1 mol% of catalyst. Moreover, this procedure has been found to be tolerant to a variety of functional groups on the aryl bromide such as formyl, propionyl, benzoyl, nitrile, and nitro

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Direct C–H arylation of 3-methoxythiophene catalyzed by Pd. Application to a more efficient synthesis of π-alkoxy-oligothiophene derivatives

Cited by 60 publications

References 13 publications

Palladium‐Catalyzed C2 or C5 Direct Arylation of 3‐Formylthiophene Derivatives with Aryl Bromides

Palladium‐Catalyzed C2 or C5 Direct Arylation of 3‐Formylthiophene Derivatives with Aryl Bromides

Regiocontroled Pd-catalysed C5-arylation of 3-substituted thiophene derivatives using a bromo-substituent as blocking group

Palladium-Catalysed C2 or C5 Direct Arylation of 3-Substituted Thiophenes with Aryl Bromides

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