Trans ‐decalin‐like sulfonium oxathiane glycosyl donors have been previously shown as a viable route to access 1,2‐ cis ‐glycosides, though these reports have indicated that donor structure has a large influence on glycosylation outcome. This work describes the synthesis of an array of methyl oxathiane donors and their subsequent use in discerning the effect of structural differences on stereoselectivity and reactivity in glycosylations. In particular, introduction of 3‐methyl groups in the oxathiane scaffold allowed kinetic tuning of the glycosyl donor without diminishing α ‐selectivity.
Warnes et al. (Fri,) studied this question.