Gr. Chen et al., Ring-closing oleflin metathesis of 3,3 '-(D-glycopyranosylidene)bis(1-propene) compounds as a route to anomeric spiro sugars, EUR J ORG C, (15), 2001, pp. 2939-2946
New peracetylated 3,3 '-(D-glycopyranosylidene)bis(1-propene), prepared fro
m peracetylated anomeric sugar dihalides and allyltributyltin in excess und
er UV irradiation conditions (AIBN, ca. 35 degreesC), lent themselves to ri
ng-closing olefin metathesis in the presence of Grubbs' catalyst (6 mol %)
to afford the corresponding peracetylated spiro[1,5-anhydro-D-glycopyranosi
tol-1,4 ' -cyclopent-1 ' -enes] (D-gluco: 81%, D-Manno: 89%, D-galacto: 72%
isolated yield), which could be deacetylated quantitatively. The bis(allyl
ation) reaction (D-gluco: 40%, D-manno: 34%, D-galacto: 24% isolated yield)
was in competition with radical-induced rearrangement and elimination reac
tions. The last process, found to be favored at higher temperature (80 degr
eesC), opens an easy route to sugar dienes difficult to prepare otherwise.