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Low-Barrier Pathway for endo-Cleavage Induced Anomerization of Pyranosides with N-Benzyl-2,3-trans-oxazolidinone Groups


Satoh, H; Hutter, J; Luethi, H P; Manabe, S; Ishii, K; Ito, Y (2009). Low-Barrier Pathway for endo-Cleavage Induced Anomerization of Pyranosides with N-Benzyl-2,3-trans-oxazolidinone Groups. European Journal of Organic Chemistry, 2009(8):1127-1131.

Abstract

Pyranosides with N-benzyl-2,3-trans-oxazolidinone undergo anomerization from the beta form to the a form even in the presence of a weak Lewis acid. Experimental evidence for endocleavage, the breaking of the bond between the pyran-oxygen and anomeric carbon atoms, in the anomerization reactions was obtained. This unexpected phenomenon was investigated by quantum mechanical calculations, which found clear differences in the transition states between anomerized and non-anomerized substrates. The computations suggest that BF3 induces endo-cleavage followed by rotation of the C1-C2 bond to give the alpha form via lower-energy transition states.

Pyranosides with N-benzyl-2,3-trans-oxazolidinone undergo anomerization from the beta form to the a form even in the presence of a weak Lewis acid. Experimental evidence for endocleavage, the breaking of the bond between the pyran-oxygen and anomeric carbon atoms, in the anomerization reactions was obtained. This unexpected phenomenon was investigated by quantum mechanical calculations, which found clear differences in the transition states between anomerized and non-anomerized substrates. The computations suggest that BF3 induces endo-cleavage followed by rotation of the C1-C2 bond to give the alpha form via lower-energy transition states.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Date:29 January 2009
Deposited On:31 Jul 2009 09:53
Last Modified:05 Apr 2016 13:18
Publisher:Wiley-Blackwell
ISSN:1099-0690
Publisher DOI:10.1002/ejoc.200801140
Permanent URL: http://doi.org/10.5167/uzh-19939

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