An efficient way to 1,7-enynes and ethyl 8-yn-2-enoates from aldohexoses and to polyhydroxylated 1-vinylcyclohexenes

In this paper, we report the synthesis of carbohydrate-derived 1,7-enynes and subsequent metathesis to yield polyhydroxylated 1-vinylcyclohexenes. For example, we converted D-glucose 2 to the (6,7)-dideoxy-D-gluco-hept-6-ene-pyranose 7, which led to the desired 1,7-enyne 16. The ring-closing metathesis of this 1,7-enyne 16 with the second generation Grubbs catalyst, under Mori's conditions, gave the corresponding polyhydroxylated 1-vinylcyclohexene 25 in 76% yield. The conversion of several aldohexoses into polyhydroxylated 1-vinylcyclohexenes was carried out with satisfying yields. We report also the synthesis of two carbohydrate-derived ethyl 8-yn-2-enoates from D-glucose derivatives.