TY - DATA T1 - Synthetic Approaches to Novel Archaeal Tetraether Glycolipid Analogues† PY - 1999/04/13 AU - Grégory Lecollinet AU - Rachel Auzély-Velty AU - Mathieu Danel AU - Thierry Benvegnu AU - Grahame Mackenzie AU - John W. Goodby AU - Daniel Plusquellec UR - https://acs.figshare.com/articles/journal_contribution/Synthetic_Approaches_to_Novel_Archaeal_Tetraether_Glycolipid_Analogues_sup_sup_/3716817 DO - 10.1021/jo9822028.s002 L4 - https://ndownloader.figshare.com/files/5808384 KW - sequential introduction KW - unsymmetrical lipids KW - monoprotected diol 35 KW - phosphate group 8 KW - dihydrocitronellyl chains KW - Pathway C KW - cyclopentane unit KW - unsymmetrical archaeal tetraether glycolipid analogues KW - Synthetic Approaches KW - saccharidic moiety KW - glycerol units KW - synthesis KW - lipid cores KW - carbohydrate units 7 KW - thermoacidophilic lipids KW - tetraether 9 KW - phosphate unit KW - sn N2 - Symmetrical and unsymmetrical archaeal tetraether glycolipid analogues have been prepared. The syntheses are based upon the elaboration of lipid cores from versatile chiral starting materials followed by simultaneous or sequential introduction of polar headgroups. Three pathways (A−C) were elaborated for the synthesis of stereochemically defined lipids 14−16 characterized by a straight bridging spacer and two dihydrocitronellyl chains attached to glycerol units at the sn-3 and sn-2 positions, respectively. Pathway C appeared to be particularly advantageous for the synthesis of tetraether 9, which possesses a cyclopentane unit as found in thermoacidophilic lipids. Diglycosylated lipids 4−6 were produced in 49−53% yields by reaction of diols 14−16 with β-d-galactofuranosyl donor 31, whereas unsymmetrical lipids possessing either two different carbohydrate units 7 or a saccharidic moiety and a phosphate group 8 were efficiently prepared from monoprotected diol 35. These compounds represent the first examples of tetraether-type analogues containing a phosphate unit and/or glycosyl moieties. ER -