Stereoselective total synthesis of acremomannolipin A and its anomer, the potent calcium signal modulators with a novel glycolipid structure: role of the stereochemistry at the anomeric center on the activity

• Published in: Tetrahedron Vol. 69; no. 47; pp. 9917 - 9930
• Main Authors: Tsutsui, Nozomi, Tanabe, Genzoh, Gotoh, Genki, Kita, Ayako, Sugiura, Reiko, Muraoka, Osamu
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 25.11.2013; Elsevier
• Subjects: Acremomannolipin A; Acremonium strictum; Calcium; Calcium signal modulator; Chemistry; Chemistry, Organic; Glycolipid; Inversions; Mannose; Modulators; Physical Sciences; Science & Technology; Selective β-mannosylation; Stereochemistry; Synthesis; Tetrahedrons; Acremomannolipin A; Selective β-mannosylation; Calcium signal modulator; Acremonium strictum; Glycolipid; TARGET; BETA-MANNOPYRANOSIDES; ANTIBIOTICS; Selective beta-mannosylation; PMK1; CONFIGURATION; ACREMONIUM; SULFOXIDES; OXIDASE; DIRECT CHEMICAL-SYNTHESIS; PURIFICATION
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2013.09.086

A full account of stereoselective total synthesis of a novel glycolipid, acremomannolipin A (1), the potent calcium signal modulator isolated from Acremonium strictum, by employing the stereoselective β-mannosylation of 4,6-O-benzylidene-protected mannosyl sulfoxide with d-mannitol as the key reaction is described. The α-anomer (epi-1) of 1 was also synthesized selectively. The calcium modulating activity was reduced upon inversion of the configuration at the anomeric center, indicating that the β-configuration of the mannose moiety is preferable for the activity. [Display omitted]