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Synlett 2011(9): 1324-1330  
DOI: 10.1055/s-0030-1260554
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Functionalized 2-Arylthiophenes with Triarylbismuths as Atom-Efficient Multicoupling Organometallic Nucleophiles under Palladium Catalysis

Maddali L. N. Rao*, Debasis Banerjee, Ritesh J. Dhanorkar
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
Fax: +91(512)2597532; e-Mail: maddali@iitk.ac.in;
Further Information

Publication History

Received 19 January 2011
Publication Date:
05 May 2011 (online)

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Abstract

Atom-efficient cross-coupling reactions of functionalized 2-bromo- and 2-iodothiophenes have been demonstrated using triarylbismuths as atom-efficient multicoupling organometallic nucleophiles under palladium-catalyzed conditions. These couplings with various functionalized triarylbismuths proceeded smoothly to afford the corresponding functionalized 2-arylthiophenes in high yields.

Key words

2-halothiophenes - cross-coupling - palladium catalysis - triarylbismuths - atom-efficient - multicoupling

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14

Representative Procedure: An oven-dried Schlenk tube under a nitrogen atmosphere was charged with 2-bromo-thiophene (0.875 mmol, 3.5 equiv, 0.143 g) followed by BiPh3 (0.25 mmol, 1 equiv, 0.110 g), K3PO4 (1.5 mmol, 6 equiv, 0.318 g), Ph3P (0.10 mmol, 0.4 equiv, 0.026 g), Pd(OAc)2 (0.025 mmol, 0.1 equiv, 0.0056 g) and anhyd DMF (3 mL). The reaction mixture was stirred in an oil-bath at 90 ˚C for 1 h. The contents were cooled to r.t., quenched with H2O (10 mL) and extracted with EtOAc (2 × 20 mL). The combined organic extracts were washed with H2O, brine, dried (MgSO4) and concentrated under reduced pressure. The crude product was purified by column chromatography using 100-200 silica gel and petroleum ether as eluent to obtain 2-phenylthiophene as a white, low melting solid (0.097 g, 81%; isolated yield based on three aryl coupling from triphenylbismuth).