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Synlett 2009(16): 2597-2600  
DOI: 10.1055/s-0029-1217959
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Pd-Catalyzed Efficient Cross-Couplings of 3-Iodochromones with Triaryl­bismuths as Substoichiometric Multicoupling Organometallic Nucleophiles

Maddali L. N. Rao*, Varadhachari Venkatesh, Deepak N. Jadhav
Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India
e-Mail: maddali@iitk.ac.in;
Further Information

Publication History

Received 11 June 2009
Publication Date:
09 September 2009 (online)

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Abstract

An efficient cross-coupling of 3-iodochromones with triarylbismuths under catalytic palladium conditions is reported. Triarylbismuths were employed as substoichiometric multicoupling nucleophiles for the synthesis of a variety of substituted isoflavones. Under the established protocol, cross-coupling reactions were found to be very efficient, furnishing high yields of products.

Key words

cross-coupling - triarylbismuths - isoflavones - palladium - catalysis - multicoupling

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12

Representative Procedure
An oven-dried Schlenk tube under nitrogen was charged with 3-iodochromone (3.3 equiv, 224.4 mg, 0.825 mmol), Ph3Bi (1 equiv, 110.0 mg, 0.25 mmol), K3PO4 (6 equiv, 318.4 mg, 1.5 mmol), PdCl2(PPh3)2 (0.09 equiv, 15.8 mg, 0.0225 mmol) followed by DME (3 mL) solvent. The reaction mixture was stirred at 90 ˚C in an oil bath for 4 h. After cooling to r.t., the contents were quenched with H2O and extracted with EtOAc (2 × 15 mL). The combined EtOAc extract was washed with 10% HCl (5 mL), brine (5 mL), and dried over anhyd MgSO4. The organic layer was concentrated in vacuo to give the crude product which was purified by column chromatography to give the 3-phenyl-4H-1-benzopyran-4-one³b (1) in 85% yield (141.7 mg).

13

In all the reactions, 3-iodochromones were employed in
0.3 equiv excess. The product yields were calculated considering all the three aryl groups for coupling from Ar3Bi. Thus, 3 equiv (0.75 mmol) of cross-coupling product corresponds to 100% yield.