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

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

References and Notes

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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-one^³b (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.