Synthesis of 2,5-Disubstituted Oxazoles from Arylacetylenes and α-Amino Acids through an I₂/Cu(NO₃)₂•3H₂O-Assisted Domino Sequence

Abstract

A new strategy has been developed for the synthesis of 2,5-disubstituted oxazoles from easily available arylacetylenes and α-amino acids in the presence of Cu(NO₃)₂•3H₂O and iodine. This reaction ­process involves the I₂/Cu(NO₃)₂•3H₂O-assisted transformation of ­arylacetylene to α-iodo acetophenone, Kornblum oxidation to phenylglyoxal, condensation to imine, decarboxylation/annulation/oxidation reaction sequence to approach 2,5-disubstituted oxazoles.

Key words

oxazoles - α-amino acids - copper catalysis - cascade reactions - alkynes

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• 26 General procedure for synthesis of 3 (3ac as an example) The mixture of phenylacetylene 1a (1.0 mmol), 2-amino-4-methylpentanoic 2c (1.0 mmol) was mixed with Cu(NO₃)₂•3H₂O (0.5 mmol), and I₂ (1.0 mmol). The mixture was heated at 60 °C in 4 mL of DMSO in a sealed vessel for 5 h till almost completed conversion of the substrates monitored by TLC analysis. Then 50 mL water was added to the mixture, which was extracted with EtOAc three times (3 × 50 mL). The extract was washed with Na₂S₂O₃ solution, dried over anhydrous Na₂SO₄ then the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (eluent: petroleum ether/EtOAc = 50/1) to afford the product 3ac” here