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Synthesis of O‐methylated glycolipids via direct stereoselective glycosidation whose sugar moieties are related to those in phenolic glycolipids (PGLs) is reported. Treatment of 2‐O‐methyl‐rhamnosyl imidates with I2 and nBu4NOTf resulted in their activation under low temperature and provided the α‐rhamnosides with excellent α‐selectivity. nBu4NOTf enhanced the electorophilicity of iodine. This methodology...