- PURIFICATION AND STRUCTURE DETERMINATION OF THREE α-D-GALACTOPYRANOSYLCYCLITOLS FROM SOYA BEAN
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Three α-D-galactopyranosylcyclitols previously isolated from soya bean are shown to be 1D-2-O-(α-D-galactopyranosyl)-4-O-methyl-chiro-inositol, 1D-5-O-(α-D-galactopyranosyl)-4-O-methyl-chiro-inositol, and 1D-2-O-(α-D-galactopyranosyl)-chiro-inositol.Assignments of the (13)C-n.m.r. spectra of these compounds and of 1L-1-O-(α-D-galactopyranosyl)-myo-inositol (galactinol) are presented.The mass spectra of derivatives prepared by permethylation or perdeuteriomethylation, followed by hydrolysis and acetylation or methylation are discussed.
- Schweizer, Thomas F.,Horman, Ian
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- A C 2-symmetric chiral pool-based flexible strategy: Synthesis of (+)- and (-)-shikimic acids, (+)- and (-)-4- epi -shikimic acids, and (+)- and (-)-pinitol
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Via combination of a novel acid-promoted rearrangement of acetal functionality with the controlled installation of the epoxide unit to create the pivotal epoxide intermediates in enantiomerically pure form, a simple, concise, flexible, and readily scalable enantiodivergent synthesis of (+)- and (-)-shikimic acids and (+)- and (-)-4-epi-shikimic acids has emerged. This simple strategy not only provides an efficient approach to shikimic acids but also can readily be adopted for the synthesis of (+)- and (-)-pinitols. These concise total syntheses exemplify the use of pivotal allylic epoxide 14 and its enantiomer ent-14. A readily available inexpensive C2-symmetric l-tartaric acid (7) served as key precursor. In general, the strategy here provides a neat example of the use of a four-carbon chiron and offers a good account of the synthesis of functionalized cyclohexane targets.
- Ananthan, Bakthavachalam,Chang, Wan-Chun,Lin, Jhe-Sain,Li, Pin-Hui,Yan, Tu-Hsin
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p. 2898 - 2905
(2014/05/06)
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- A new stereoselective approach to a selectively protected derivative of d-pinitol and its evaluation as α-l-rhamnopyranose mimetic
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The synthesis of 3,5-di-O-benzyl-d-pinitol has been stereoselectively accomplished through intramolecular aldolization of 2,6-di-O-benzyl-4-O-methyl-l-lyxo-hexos-5-ulose followed by reduction with NaBH(OAc)3. Computational analysis [DFT calculations at the B3LYP/6-31G(d) level] suggests that d-pinitol in water largely prefers the conformation corresponding to the 1C4 one of a α-l-rhamnopyranoside unit, being thus a good candidate for its mimicking.
- Catelani, Giorgio,D'Andrea, Felicia,Griselli, Alessio,Guazzelli, Lorenzo,Legnani, Laura,Toma, Lucio
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p. 4534 - 4536
(2008/09/21)
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- Stereoselective oxidation of protected inositol derivatives catalyzed by inositol dehydrogenase from Bacillus subtilis
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Inositol dehydrogenase (EC 1.1.1.18) from Bacillus subtilis is shown to have a nonpolar cavity adjacent to the active site, allowing racemic protected inositol derivatives such as 4-O-benzyl-myo-inositol to be recognized with very high apparent stereoselectivity.
- Daniellou, Richard,Phenix, Christopher P.,Tam, Pui Hang,Laliberte, Michael C.,Palmer, David R. J.
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p. 401 - 403
(2007/10/03)
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- Stereochemical observations on the bromate induced monobromopentahydroxylation of benzene by catalytic photoinduced charge transfer osmylation. A concise synthesis of (±)-pinitol
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The use of lower temperatures in the title reaction favours the formation of the neo diastereoisomer of the deoxybromoinositol whose diisopropylidene derivative can be converted in three steps to (±)-pinitol.
- Jung, Pierre M. J.,Motherwell, William B.,Williams, Alvin S.
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p. 1283 - 1284
(2007/10/03)
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- Total synthesis of (+)-pinitol
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A new synthesis of (+)-pinitol 9 has been developed starting from the 7-oxanorbornenic sulfone (+)-5, prepared in enantiomerically pure form by resolution of the sulfonyl-7-oxanorbornanol 4. These precursors are available from the Diels-Alder adduct of furan and trans-1,2-bis-(phenylsulfonyl)-ethylene.
- Acena, Jose Luis,Arjona, Odon,Plumet, Joaquin
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p. 3535 - 3544
(2007/10/03)
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- An effective strategy for the synthesis of 6-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-chiro- and -D-myo-inositol 1-phosphate related to putative insulin mimetics
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Two glycosylinositol phosphates related to putative insulin mimetics, 6-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-chiro-inositol 1-phosphate (1) and 6-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-myo-inositol 1-phosphate (2), have been synthesized from selectively protected and enantiomerically pure D-chiro- and myo-inositol derivatives. The D-chiro-inositol unit was prepared in a multigram scale from D-glucose using the Ferrier's carbocyclization route, and it was transformed into the corresponding myo epimer by an oxidation-reduction sequence. The trichloroacetimidate method was applied efficiently for the key glycosylation of the inositol derivatives.
- Jaramillo,Chiara,Martin-Lomas
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p. 3135 - 3141
(2007/10/02)
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- Biocatalysis as a Rational Approach to Enantiodivergent Synthesis of Highly Oxygenated Compounds: (+)- and (-)-Pinitol and Other Cyclitols
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Bacterial oxygenation of halogenated aromatic compounds yields arene cis-diols of type 2 of high enantiomeric purity.Further oxygenation of these extremely versatile synthetic intermediates provides for stereo- and regioselective introduction of additional functionalities such as hydroxyl groups.Several rational methods of oxygenation (epoxidation, osmylation, singlet oxygen addition, and ozonolysis) are used to produce, in short synthetic routes, cyclitol derivatives of medicinal importance.Proper symmetry considerations lead to the development of enantiodivergent synthetic design of target compounds from a single enantiomer of a starting diol.These principles are ilustrated on the short syntheses of (+)- and (-)-pinitol.Stereocontrolled oxidative transformation of diols of type 2 are exemplified in the synthesis of conduritol C and dihydroconduritol C.Full experimental details are provided for all compounds.A guide to the stereorational design of any stereoisomer of cyclohexane (poly)ols or carbohydrates is provided at the end of the paper.
- Hudlicky, Tomas,Rulin, Fan,Tsunoda, Toshiya,Luna, Hector,Andersen, Catherine,Price, John D.
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p. 229 - 238
(2007/10/02)
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- Approaches to the synthesis of glycosyl phosphatidyl inositols. Enantioselective synthesis of optically active chiro- and myo-inositols
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An efficient synthetic strategy to optically active conveniently substituted D-chiro (5) and D-myo-inositol (10) derivatives has been developed starting from methyl α-D-glucopyranoside. Compounds 5 and 10 constitute valuable intermediates for the preparation of glycosyl phosphatidyl inositols.
- Jaramillo,Martin-Lomas
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p. 2501 - 2504
(2007/10/02)
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- Mikrobial Oxidation in Synthesis: Preparation of (+)- and (-)-Pinitol from Benzene
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Microbial oxidation with Pseudomonas putida of benzene affords cis-1,2-dihydroxycyclohexa-3,5-diene (2) which may be converted in five steps and 49percent overall yield to (+/-)-pinitol.Resolution of an intermediate alcohol (6) with menthoxyacetyl chloride provides optically pure materials which may be independently transformed to (+)- or (-)-pinitol.Demethylation conditions for pinitol together with further reactions of (2) and related compounds were investigated.
- Ley, Steven V.,Sternfeld, Francine
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p. 3463 - 3476
(2007/10/02)
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- PHOTOCHEMICAL ROUTES FROM ARENES TO INOSITOL INTERMEDIATES: THE PHOTO-OXIDATION OF SUBSTITUTED cis-CYCLOHEXA-3,5-DIENE-1,2-DIOLS
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Endoperoxides such as (6), (15), (16) and (20) are avaliable by microbial oxidation and photo-oxidation of arenes; u.v. photolysis of (6) yields mainly the βc-epoxyketone (9), and further photolysis gives (10) via photoepimerisation.
- Carless, Howard A.J.,Billinge, Jacqueline R.,Oak, Ozer Z.
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p. 3113 - 3116
(2007/10/02)
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- The Allyl Group for Protection in Carbohydrate Chemistry. Part 18. Allyl and Benzyl Ethers of myo-Inositol. Intermediates for the Synthesis of myo-Inositol Triphosphates
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Racemic 1,2:4,5-di-O-isopropylidene-myo-inositol was converted into racemic 1,2,4-tri-O-benzyl-myo-inositol, 1,2,4-tri-O-p-methoxybenzyl-myo-inositol and 2,4,5-tri-O-benzyl-myo-inositol using allyl groups for 'temporary' protection.The benzyl ethers are required as intermediates for the synthesis of the 'second messenger', inositol 1,4,5-triphosphate and its metabolite, inositol 1,3,4-triphosphate. 1,2,3,4-Tetra-O-benzyl-myo-inositol, and its two monoallyl and monoprop-1-enyl ethers, were also prepared as model compounds for phosphorylation studies of the vicinal 5,6-diol system which occurs in 1,2,4-tri-O-benzyl-myo-inositol.
- Gigg, Jill,Gigg, Roy,Payne, Sheila,Conant, Robert
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p. 423 - 430
(2007/10/02)
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- MICROBIAL OXIDATION IN SYNTHESIS: A SIX STEP PREPARATION OF (+/-)-PINITOL FROM BENZENE
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Synthesis of (+/-)-pinitol in 35percent overall yield from benzene has been achieved where the key step involved microbial oxidation of benzene to cis-1,2-dihydroxycyclohexa-3,5-diene.
- Ley, Steven V.,Sternfeld, Francine,Taylor, Stephen
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p. 225 - 226
(2007/10/02)
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- NOVEL BIOSYNTHESIS OF D-PINITOL IN SIMMONDSIA CHINENSIS
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Chase experiments with 14CO2 and feeding experiments with labwelled inositols showed that D-pinitol in leaves of Simmondsia chinensis arises via epimerization of D-ononitol.This finding represents an alternative pathway, since D-pinitol is formed in gymnosperms and other plants by epimerization of sequoyitol.Key Word Index -- Simmondsia chinensis; Simmondsiaceae; jojoba; biosynthesis; cyclitols; D-pinitol; D-ononitol.
- Dittrich, Peter,Korak, Andrea
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