Total Syntheses of Conformationally Locked Difluorinated Pentopyranose Analogues and a Pentopyranosyl Phosphate Mimetic

Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a
difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal
intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates
followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers
novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a
glycosyl phosphate.

三氟乙醇通过一系列紧凑的合成步骤被制备，包括金属化的二氟烯醇、二氟烯丙醇、[2,3]-维蒂格重排，最终通过环氧化合物（RCM）反应，并仅需进行最低限度的中间体纯化，得到一系列环辛烯酮中间体。对这些中间体进行环氧化反应，随后通过跨环开环或二羟基化，进而进行跨环半缩醛化，从而得到新颖的环状双环戊吡喃糖类似物，其中一种（在一种情况下）被进一步制备为糖苷磷酸类似物。