Publication

Total asymmetric synthesis of doubly branched carba-hexopyranoses and amino derivatives starting from the Diels-Alder adducts of maleic anhydride to furfuryl esters

Pierre Vogel
1999
Journal Articles

Abstract

The Diels-Alder adducts of maleic anhydride to furfuryl esters were reduced into 7-oxabicyclo[2.2.l]hept-5-ene-1.2-exo,3-exo-trimethanol (+/-)-15 and enantiomerically pure (-)-15 (Scheme 1). The tripivalate of (+/-)-15 was converted into (1RS,2RS,3RS,4RS,5SR,6SR)-1,5,6-tris(hydroxymethyl)cyclohexane-1,2,3,4-t etrol ((+/-)-23; Scheme 2). Reaction of BBr3 with the triacetate (+/-)-30 of (+/-)-15 gave (1RS,2RS,5RS,6RS)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate ((+/-)-31) at -78 degrees, and (1RS,2RS,5SR,8SR)-2-endo-hydroxy-6-oxabicylo[3.2.l]oct-3-ene-5,8-dimethy l diacetate ((+/-)-32) at 0 degrees (Scheme 3). Single-crystal X-ray diffraction of (1RS,2RS,5SR,8SR)-2-acetoxy-6-oxabicyclo[3.2.1]oct-3-ene-5,8-dimethyl diacetate ((+/-)-33) was carried out. Displacement of bromide (+)-31 (derived from (-)-15) with azide anion gave (+)-38 which was transformed into (+)-( 1R,2R,5S,6S)-5-amino-6-hydroxycyclohex-3-ene-1,2,3-trimethanol ((+)-40) (Scheme 4). Reaction of (+/-)-31 with BBr3 at 0 degrees, followed by azide disubstitution led to (1RS,2RS,5SR,6SR)-5-amino-3-(aminomethyl)-6-hydroxycyclohex-3-ene-1,2-di methanol ((+/-)-45). Dihydroxylation of (+/-)-38 and further transformations gave (1RS,2RS,3SR,4RS,5SR,6RS)-5-amino-1,4,6-trihydroxycyclohexane-1,2,3-trim ethanol ((+/-)-49) and (1RS,2RS, 3SR,4RS,5SR,6RS)-2,3-dihydroxy-7-oxabicyclo[4.1.0]heptane-2,3,4-trimetha nol ((+/-)-55) (Schemes 5 and 6). Expoxidation of the 4-nitrobenzoate (+/-)-61 of (+/-)-38 allowed the preparation of (1RS,2RS,3SR,4RS,5RS)-5-amino-4-amino-1.4-dihydroxycyclohexane-1,2,3-tri methanol ((+)-65) and of (1RS,2RS,3SR,4RS,5SR,6RS)-5-amino-4-hydroxy-7-oxabicyclo[4.1.0]heptane-1 ,2,3 ((+/-)-67) (Scheme 7). The new unprotected polyols and aminopolyols were tested for their inhibitory activity toward commercially available glycohydrolases. At 1 mM concentration, 34, 30, and 31% inhibition of beta-galactosidase from bovine liver was observed for (+/-)-40, (+/-)-65, and (1)-67, respectively.

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https://infoscience.epfl.ch/entities/publication/4b72f57b-761d-4184-9c81-6b2fcbe7548a

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Pierre Vogel
1999
Journal Articles

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/4b72f57b-761d-4184-9c81-6b2fcbe7548a

Related concepts (31)

Amino acid

Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although over 500 amino acids exist in nature, by far the most important are the α-amino acids, from which proteins are composed. Only 22 α-amino acids appear in the genetic code of all life. Amino acids can be classified according to the locations of the core structural functional groups, as alpha- (α-), beta- (β-), gamma- (γ-) or delta- (δ-) amino acids; other categories relate to polarity, ionization, and side chain group type (aliphatic, acyclic, aromatic, containing hydroxyl or sulfur, etc.

Enantiomer

In chemistry, an enantiomer (/ɪˈnænti.əmər, ɛ-, -oʊ-/ ih-NAN-tee-ə-mər; from Ancient Greek ἐνάντιος (enántios) 'opposite', and μέρος (méros) 'part') – also called optical isomer, antipode, or optical antipode – is one of two stereoisomers that are non-superposable onto their own . Enantiomers are much like one's right and left hands, when looking at the same face, they cannot be superposed onto each other. No amount of reorientation in three spatial dimensions will allow the four unique groups on the chiral carbon (see chirality) to line up exactly.

Iodine

Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a violet gas at . The element was discovered by the French chemist Bernard Courtois in 1811 and was named two years later by Joseph Louis Gay-Lussac, after the Ancient Greek Ιώδης 'violet-coloured'. Iodine occurs in many oxidation states, including iodide (I−), iodate (IO3-), and the various periodate anions.

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