176540-24-2Relevant academic research and scientific papers
Total, asymmetric synthesis of methyl 3-deoxy-3-(1',2',6'-trideoxy- 2',6'-imino-D-galactitol-1-yl)-α-D-manno-pyranoside (A C-linked imino disaccharide): Conformational analysis and glycosidase inhibition
Marquis, Christian,Picasso, Sylviane,Vogel, Pierre
, p. 1441 - 1452 (1999)
The lithium enolate 16 derived in 5 steps from the Diels-Alder adduct of furan to 1-cyanovinyl (1S)-camphanate [(+)-12: a 'naked sugar' of the first generation] was reacted with (+)(1R, 4S,5S,6S)-6-endo-chloro-3-methylidene-5- exo-phenylseleno-7-oxabicyclo[2.2.1 ]heptan-2-one [(+)-8] to give a unique product of Michael addition after acidic quenching. This adduct (-)-18 was transformed into branched long-chain carbohydrate derivatives such as benzyl 5-deoxy-5-[(5'-O-acetyl-3'-deoxy-2'-O-methoxymethyl-D-manno-furanurono-6,1- lactone-3-yl)methyl]-(tert- butyl)dimethylsilyl-2,3-di-O-methoxymethyl-α and β-L-gulo-furanosideuronate [(-)-27]. Hydrogenolysis, followed by a Curtius rearrangement permitted to construct the corresponding branched 5- amino-5,6-dideoxydodecose derivative (-)-30 which was converted into 5-O- acetyl-3-[5'-N-(benzyloxy)carbonyl-2',3'-di-O-methoxymethyl-α and β-D- manno-furanose]-2-O-methoxymethyl-D-manno-furanurono-6,1-lactone [(-)-31] and then into methyl 3-deoxy-3-(1',2',6'-trideoxy-2',6'-imino-D-galactitol-1'- yl)-α-D- manno-pyranoside [(-)-1]. Its 1H NMR spectrum measured at variable temperature demonstrated that (-)-1 exist as a double equilibrium involving two pairs of rotamers about the σC(1')-C(2') and cvC(1')-C(3) bond [CH2 bridge linking β-C(1) of the 1,5-dideoxy-1,5-imino-D-lyxitol unit at C(3) of methyl α-D-manno-pyranoside]. Rotamers B' in which C(3) is gauche with respect to C(3') is preferred to conformers C' in which C(3) is anti with respect to C(3'). An equilibrium constant K (B' = C') =- 0.35 (25 °C) was evaluated. Rotamers B [C(2) gauche with respect to C(2')] and C [C(2) anti with respect to C(2')] are equally populated. Disaccharide mimetic (-)-1 is a moderate inhibitor of α-L-fucosidases from bovine liver (K(i) = 100 μM) and human placenta.
Total asymmetric synthesis of long-chain, branched carbohydrates and of an Aza-C-disaccharide
Frerot, Eric,Marquis, Christian,Vogel, Pierre
, p. 2023 - 2026 (2007/10/03)
Michael addition of (-)-(1S,5R,6R,7S)-6,7-bis(methoxymethoxy)-2,8-dioxabicyclo[3.2.1]octan -3-one lithium enolate to (+)-(1R,4S,5S,6S)-5-benzeneselenyl-6-chloro-3-methylidene-7-oxabicyclo [2.2.1]heptan-2-one gives a single adduct with high stereoselectivity. It was converted into a derivative of β-D-(1 ← 3)-C-linked 1,5-dideoxy-1,5-imino-lyxopyranoside of α-D-mannofuranurono-6,1-lactone and other long-chain, branched sugars.
