Total synthesis of the antiallergic naphtho-alpha-pyrone tetraglucoside, cassiaside C(2), isolated from cassia seeds.
Toralactone 9-O-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl-(1-->3)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranoside (1, cassiaside C(2)), isolated from Cassia obtusifolia L. and showing strong antiallergic activity, was concisely synthesized employing glycosyl trifluoroacetimidates as glycosylation agents. The unique naphtho-alpha-pyrone structure of toralactone (5) was constructed by condensation of orsellinate 8 with pyrone 9 in the presence of LDA as developed by Staunton and co-workers. The naphthol of toralactone showed minimal reactivity as an acceptor and was screened with various glycosyl donors. It is finally concluded that sacrifice of an excess amount of the trifluoroacetimidate or trichloroacetimidate donors (6f/6g, 6.0 equiv) in the presence of a catalytic amount of TMSOTf (0.05 and 0.3 equiv, respectively) afforded excellent yields of the coupling product, which was otherwise only a minor product under a variety of conditions examined.
Zhang
Zhaojun
Z
State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China.
Yu
Biao
B
D018926:Anti-Allergic Agents / Q000138:chemical synthesis* / Q000494:pharmacology; D002240:Carbohydrate Sequence; D002366:Cassia / Q000737:chemistry*; D002384:Catalysis; D006031:Glycosylation; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000138:chemical synthesis* / Q000494:pharmacology; D011753:Pyrones / Q000138:chemical synthesis* / Q000494:pharmacology; D012639:Seeds / Q000737:chemistry
D018926:Anti-Allergic Agents; D007202:Indicators and Reagents; D009844:Oligosaccharides; D011753:Pyrones; C115840:toralactone 9-O-glucopyranosyl-(1-6)-O-glucopyran osyl-(1-3)-O-glucopyranosyl-(1-6)-O-glucopyranoside