- Transformation of cyclohexene to enantiopure cyclitols mediated by sequential oxyselenenylation with (S,S)-hydrobenzoin: Synthesis of D-chiro-inositol and muco-quercitol
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Oxyselenenylation of cyclohexene with (S,S)-hydrobenzoin and subsequent oxidation-elimination allows isolation of an allylic ether in which further phenylselenenylation is completely regioselective, thus allowing entry to the cyclitols D-chiro-inositol and muco-quercitol.
- Kim, Kwan Soo,Park, Jong H.,Moon, Hoi Kyung,Yi, Hann
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p. 1945 - 1946
(2007/10/03)
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- Microbial Oxidation of Aromatics in Enantiocontrolled Synthesis. Part 1.Expedient and General Asymmetric Synthesis of Inositols and Carbohydrates via and Unusual Oxidation of a Polarized Diene with Potassium Permanganate
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This paper reports on the details of a general design of carbohydrates and cyclitols from biocatalytically derived synthons.Homochiral 1-halogenocyclohexa-4,6-diene-2,3-diols 1a and 1b have been generated from chloro- and bromobenzene, respectively, by means of bacterial dioxygenase of Pseudomonas putida 39D.These chiral synthons have been manipulated to cyclitols and carbohydrates by further stereoselective functionalizations.The preperation of D-chiro-inositol, neo-inositol, muco-inositol, and allo-inositol exemplifies their use in enantiocontrolled synthesis.A novel oxidation of polarized dienes with KMnO4 resulted in the synthesis of α-halogeno epoxy diols, which proved unexpectedly stable.A mechanism is proposed for this transformation and placed in context with the only four reported examples of this reaction in the literature.In addition to the application of this new chemistry to the synthesis of cyclitols, chloro epoxy diol 21a has been transformed into a series of cyclitol synthons by reductive or hydrolytic operations.Reaction of 21a with ammonia led to the preparation of highly oxygenated pyrazines, whose structure were proven by X-ray crystallography.The use of 21a in the preparation of D-chiro-3-inosose, a hitherto unreported cyclitol derivative, is also reported.In addition, chloro epoxy diol 21a was transformed into D-erythruronolactone, completing the synthesis of this important chiral pool reagent in two operations from chlorobenzene.Oxidative cleavage of tetrol 20 yielded D-mannosolactone identical with an authentic sample.
- Hudlicky, Tomas,Mandel, Martin,Rouden, Jacques,Lee, Robert S.,Bachmann, Bryan,et al.
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p. 1553 - 1568
(2007/10/02)
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- Optically active phenoxypropionic esters
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Optically active compounds of the formula I STR1 where R is C1 -C12 -alkyl or -perfluoroalkyl in which one or two non-adjacent CH2 or CF2 groups can also be replaced by --O-- and/or --CO-- and/or --CO--O-- and/or --CH=CH-- and/or --CH-halogen-- and/or --CHCN-- and/or --0--CO--CH-halogen-- and/or --O--CO--CHCN--, or is C1 -C12 -alkyl which can have a terminal chemically reactive group and in which a CH2 group can be replaced by --O--, A1 and A2 are each, independently of one another, 1,4-phenylene which is unsubstituted or substituted by one or two F and/or Cl and/or Br atoms and/or CH3 groups and/or CN groups and in which one or two CH groups can also be replaced by N, 1,4-cyclohexylene in which one or two non-adjacent CH2 groups can also be replaced by --O-- and/or --S--, 1,4-piperidinediyl, 1,4-bicyclo[2.2.2]octylene, 2,6-naphthalenediyl, decahydro-2,6-naphthalenediyl or 1,2,3,4-tetrahydro-2,6-naphthalenediyl, A3 is unsubstituted or substituted phenyl, Z is --CO--O--, --O--CO--, --CH2 CH2 --, --OCH2 --, --CH2 O--, --C C-- or a single bond and m is 0, 1, 2 or 3.
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- General Synthesis of Inositols by Hydrolysis of Conduritol Epoxides Obtained Biocatalytically from Halogenobenzenes: (+)-D-chiro-Inositol, allo-Inositol, muco-Inositol and neo-Inositol
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Four of the nine isomeric inositols have been prepared by hydrolytic opening of epoxides derived from 3-halogenocyclohexa-3,5-diene-1,2-diol by further oxidation with potassium permanganate or by reduction of chiro-3-inosose (2L-2,3,6/4,5-pentahydroxycyclohexanone).
- Mandel, Martin,Hudlicky, Thomas
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p. 741 - 744
(2007/10/02)
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- GLYCOSYL-INOSITOL DERIVATIVES III. SYNTHESIS OF HEXOSAMINE-INOSITOL-PHOSPHATES RELATED TO PUTATIVE INSULIN MEDIATORS
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The disaccharides related to glycosyl phosphatidyl inositol anchors of membrane proteins, 4-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-myo-inositol-1-phosphate and 4-O-(2-amino-2-deoxy-α-D-galactopyranosyl)-D-chiro-inositol-1-phosphate, have been prepared from optically resolved myo-inositol derivatives.The chiro-inositol moiety was obtained by epimerization of a selectively blocked myo-inositol-triflate ester.The resolved inositols were subsequently phosphorylated to yield the disaccharide aglycones.The amino-sugar components were prepared by azidonitration of suitably protected glucal and galactal derivatives.The derived pyranosyl chlorides were then condensed with the inositol phosphates using silver triflate as the promoter.
- Berlin, William K.,Zhang, Wen-Sheng,Shen, T. Y.
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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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- 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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