Aromatic Helical Foldamers as Nucleophilic Catalysts for the Regioselective Acetylation of Octyl β-d-Glucopyranoside

Two indolocarbazole-naphthyridine foldamers 2 and 3 that fold into helical conformations were prepared. The 4-(N,N-dimethylamino)pyridine (DMAP) moiety was introduced at one end of the foldamer strands to develop foldamer-based catalysts for the site-selective acylation of polyols. These foldamers adopt helical conformations containing internal cavities capable of binding octyl β-d-glucopyranoside. The association constants were determined to be 1.9 (±0.1)×10⁵ M⁻¹ for 2 and 2.1 (±0.1)×10⁵ M⁻¹ for 3 in CH₂Cl₂ at 25 °C. In the presence of DMAP, 2 or 3 as the catalysts, octyl β-d-glucopyranoside was subjected to acetylation under identical reaction conditions. The DMAP-catalysed reaction afforded the random distribution of the monoacetylates (6-OAc : 4-OAc : 3-OAc : 2-OAc=33 : 24 : 41 : 2). In contrast, foldamers 2 and 3 led to the predominant formation of 6-OAc. The relative distributions were estimated to be 6-OAc : 4-OAc : 3-OAc=88 : 4 : 6 : ∼0 with 2 and 6-OAc : 4-OAc : 3-OAc : 2-OAc=90 : 3 : 6 : 1 with 3.