Efficient catalytic effects of Lewis acids in the 1,3-dipolar cycloaddition reactions of carbonyl ylides with imines.
[reactions: see text] 1,3-Dipolar cycloaddition reactions between imines and carbonyl ylides generated by tandem intramolecular carbenoid-carbonyl cyclizations were found to be effectively catalyzed by Lewis acids (10 mol %). The Rh2(OAc)4-catalyzed reactions of o-(methoxycarbonyl)-alpha-diazoacetophenone with imines such as N-[2-(benzyloxy)benzylidene]aniline in the absence of Lewis acid gave no 1,3-dipolar cycloaddition products, but rather the dimeric product of the corresponding carbonyl ylide. In contrast, in the presence of Lewis acids such as Yb(OTf)3, the 1,3-dipolar cycloaddition reactions of the corresponding 1-methoxy-2-benzopyrylium-4-olate proceeded smoothly with several imines, giving in most cases exo-selectivity and no formation of the dimeric product. When Yb(OTf)3 was used as a Lewis acid catalyst, a fundamental catalytic effect was also observed in the cycloaddition reactions of imines with carbonyl ylides generated from 1-diazo-5-phenyl-2,5-pentanedione, 1-diazo-2,5-hexanedione and diazomethyl 2,3,4,5-tetrachloro-6-methoxycarbonylphenly ketone. This efficient catalytic effect can be satisfactorily explained in terms of energetics of the cycloaddition in the absence and the presence of Lewis acid by calculations using the ONIOM (B3LYP/6-31G(d):PM3) method.
Suga
Hiroyuki
H
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380-8553, Japan. sugahio@shinshu-u.ac.jp
Ebiura
Yasutaka
Y
Fukushima
Kazuaki
K
Kakehi
Akikazu
A
Baba
Toshihide
T