Synthesis of orthogonally protected d-olivoside, 1,3-di-O-acetyl-4-O-benzyl-2,6-dideoxy-d-arabinopyranose, as a C-glycosyl donor

1,3-Di-O-acetyl-4-O-benzyl-2,6-dideoxy-d-arabinopyranose (11) was synthesised from thiophenyl α-d-mannopyranoside (21) in an eight-step sequence. Tosylation of 21 and subsequent reaction with 2,2-dimethoxypropane gave tosylate 22, which upon treatment with lithium aluminium hydride furnished 6-deoxy glycoside 24 and by-product thiophenyl 6-deoxy-2-O-isopropyl-α-d-arabinopyranoside. The X-ray crystal structure of the latter was determined. Benzylation of the 4-hydroxyl group of 24 and subsequent protecting group manipulation gave d-rhamnosyl bromide 29, which on treatment with zinc–copper couple gave the orthogonally protected d-rhamnal 30. Triphenylphosphine hydrogen bromide catalysed addition of acetic acid to 30 furnished the target molecule 11. The scandium(III) triflate promoted reaction of 11 and 2-naphthol gave the corresponding C-glycoside 36 in 86% yield.

Differentially protected 2,6-dideoxyglycosyl donor 11 was synthesized from thiophenyl α-d-mannopyranoside (21) in an eight-step sequence. Its Sc(OTf)3 catalysed reaction with 2-naphthol gave β-C-glycoside 36 in 86% yield.Figure optionsDownload as PowerPoint slide