The effects of Lewis acid on the 1,3-dipolar cycloaddition reaction of C-arylaldonitrones with alkenes.
The regio- and stereoselectivity of the 1,3-dipolar cycloaddition reactions of C-aryl-N-alkylaldonitrones (1a-e) with some alkenes were found to be affected significantly by the addition of Lewis acid. The rate of the reaction was also affected by adding the Lewis acid. In the reactions using allyl alcohol as a dipolarophile an addition of Lewis acid caused a remarkable acceleration of the reaction and a great change in the stereoselectivity. In the reactions using ethyl acrylate as a dipolarophile the regioselectivity was reversed whether the reaction was performed in the presence or the absence of Lewis acid; i.e. isoxazolidine-5-carboxylates were obtained mainly in the absence of Lewis acid although isoxazolidine-4-carboxylates were obtained mainly in the presence of Lewis acid. When the reaction of C,N-diarylaldonitrones (1k, 1m, 1n) with ethyl acrylate was carried out in the presence of Lewis acid, the cleavage of the N-O bond of the cycloadducts giving gamma-aminoalcohols was also observed besides a reverse phenomenon of regioselectivity.
Shimizu
Tomio
T
Kyoto Institute of Technology, Faculty of Engineering, Materials Science, Kyoto, Japan. shimizu@chem.kit.ac.jp
Ishizaki
Masaya
M
Nitada
Nobuo
N
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003500:Cyclization; D007202:Indicators and Reagents; D007555:Isoxazoles / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D009589:Nitrogen Oxides / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D007202:Indicators and Reagents; D007555:Isoxazoles; D009589:Nitrogen Oxides; C015388:nitrones