Preferential formation of cis-4,5-dihydrooxazole derivatives via photoinduced electron transfer-initiated cyclization of N-acyl-α-dehydroarylalanine alkyl esters

Abstract

The alkyl, aryl, and acyl substituent effects on the photoinduced electron transfer-initiated cyclization reaction of the title compounds ( 1) were investigated in polar solvents from mechanistic and synthetic points of view. The irradiation of ( Z)- 1 in methanol containing triethylamine (TEA) was found to quantitatively give cis- and trans-4,5-dihydrooxazole derivatives ( cis- 2 and trans- 2). In addition to thermodynamic considerations for electron transfer and fluorescence quenching in the presence of TEA, acyl and aryl substituent effects on the emission intensity and photoreactivity of 1 confirmed the involvement of consecutive electron transfer reactions that form ( E)-arylmethylene radical anion and ( E)- N-acyl radical anion intermediates. It was also confirmed that the cyclization of the latter intermediate eventually leads to 2. On the basis of the finding that the selectivity for cis- 2 is greatly increased with increasing the steric bulkiness of alkyl and aryl substituents in 1, it was concluded that steric hindrance of these substituents toward hydrogen shift in the cyclized biradical intermediate, precursor of 2, is responsible for the kinetically controlled hydrogen shift in this intermediate. A product composition analysis showed that the protic polar solvent, methanol, of hydrogen-bonding solvation ability is a most suitable solvent for the photocyclization reactions examined.