Rules and stereoelectronic guidelines for the anionic nucleophilic displacement of furanoside and furanose O-sulfonates.

Rules for predicting anionic SN2 displacement viability in furanose and furanoside sulfonates are presented.

An update of the rules for pyranoside sulfonate displacement.

The original 1967 Richardson-Hough rules for predicting SN2 displacement viability in carbohydrate sulfonate derivatives with external nucleophiles have now been updated. Not only do the original rules still hold, but the newly updated rules rationalize why O-triflates (trifluoromethanesulfonate esters) frequently allow many seemingly "disallowed" pyranosidic nucleophilic substitutions to proceed. The new guidelines, which are based on three decades of experimental evidence, allow the feasibility of many pyranosidic O-triflate SN2 displacements to be gauged beforehand.