D. Kiely, C. Cantrell, J. M. Riordan
Feb 8, 1983
Citations
0
Influential Citations
2
Citations
Journal
Journal of Carbohydrate Chemistry
Abstract
Abstract Mild treatment of 3,4,5-tri-O-acetyl-1,7-dibromo-1,7-dideoxyxylo-2,6-heptodiulose (2) with acetate ion in several solvents produced unsaturated, branched, six-membered carbocyclic compounds. 4S(R),5R(S),6R(S)-6-acetoxy-4-bromomethyl-4,5-epoxy-6-ethoxy-2-cyclohexenone (3) was the predominant cyclization product in ethanol solution, and the 6-methoxy analog (4) was the major product in methanol solution. Cyclization of 2, in acetone cleanly produced the cross-conjugated ketone 4S(R)-2-acetoxy-3-bromo-4-bromomethyl-4-hydroxy-2,5-cyclohexadien-1-one (5), and cyclization of the 1,7-dichloro analog of 2, compound 9, gave the corresponding dichlorocyclohexadien-1-one 11. Compound 8, the 4-O-acetyl derivative of 5, and 2,3,4,6-tetraacetoxybenzyl acetate (7) were derived from 2 in an acetic anhydride—potassium acetate mixture while the deoxycyclose D,L-(3,4,6/5)-4,5,6-tri-O-acetyl-3-C(iodomethyl)-3,4,5,6-tetrahydroxycyclohexanone (12) was the reductive cyclization product from treatment of an acetone solu...