Synthesis of 1,2-trans-disaccharides via sugar thio-orthoesters

The reaction of sugar 1,2-thio-orthoesters in the d-gluco, d-galacto, d-manno, and l-rhamno series with primary and secondary trityl ethers of monosaccharides, in the presence of triphenylmethylium perchlorate as catalyst, affords, stereospecifically, derivatives of 1,2-trans-disaccharides in good yields. 4-Trityl ethers of benzyl 2-acetamido-3,6-di-O-acetyl-2-deoxy-α-d-glucopyranoside and methyl 2,3,6-tri-O-benzoyl-α-d-galactopyranoside exhibit low reactivity in glycosylation by thio-orthoesters. A reaction scheme for the glycosylation is discussed.