This paper investigates the origin of the anomalous anomeric effect in merosinigrin, a 2- cyanothiane in which the cyano group is axial as expected for the anomeric effect, but in which bond distances are opposite to that expected from the nS→ σ C-CN* orbital interaction, which underlies the classical anomeric effect. The model compounds, 2- cyanooxane, 2-cyanothiane, and 2-cyanoselenane, were synthesized and studied both ...
