Synthesis of chiral oxepanes and pyrans by 3-O-allylcarbohydrate nitrone cycloaddition (3-OACNC)

3-O-Allylearbohydrate nitrone cycloaddition (3-OACNC) furnished pyran and oxepane derivatives from 3-O-ally hexose N-benzyl nitrones and 3-O-allyl furanoside-5-aldehyde N-benzyl/methyl nitrones. The regioselectivity of 3-OACNC was found to depend on the following factors (a) the structural nature of the nitrone (b) substitution and stereochemistry at 3-C of the carbohydrate backbone (c) substitution at the terminus of the O-allyl moiety. Oxepanes or pyrans obtained from a particular set of a hexose nitrone and the corresponding furanoside nitrone were converted to enantiomeric cyclic ethers through degradation. A mixture of an oxepane and a pyran was formed in the intramolecular oxime olefin cycloaddition (IOOC) of a 3-O-allylcarbohydrate derived oxime. (C) 2003 Elsevier Science Ltd. All rights reserved.