576-63-6Relevant academic research and scientific papers
Orthogonally protected cyclohexanehexols by a "one reaction - One product" approach: Efficient access to cyclitols and their analogs
Jagdhane, Rajendra C.,Shashidhar, Mysore S.
supporting information; experimental part, p. 2945 - 2953 (2010/08/07)
Differentially protected myo-inositol derivatives were prepared from commercially available myo-inositol through regioselective O-alkylation reactions, which give a single product in each step. These derivatives were converted into six isomeric inositol derivatives carrying orthogonal hydroxy protecting groups. For all these reactions, conditions were chosen to prevent the formation of isomeric products, which obviates the need for separation of isomers and provides the required cyclitol derivative in very good yields. The synthetic potential of these derivatives was illustrated by the conversion of some of the orthogonally protected inositol derivatives into other cyclitol derivatives. Isomeric inositols were also prepared by the global deprotection of all the hydroxy groups.
Novel synthesis of enantiomerically pure natural inositols and their diastereoisomers
Takahashi,Kittaka,Ikegami
, p. 2705 - 2716 (2007/10/03)
The various inositol polyphosphates have been found to trigger many important biological processes. Although the knowledge of this phosphoinositide signaling system has been discovered in the past 10 years, many factors remain unclear. For this reason, there is an increased demand for supplies of D-myo-inositol and particularly of novel analogues to investigate these biological mechanisms in more detail. Herein, we report the efficient syntheses of all diastereoisomers of inositol starting with 6-O-acetyl-5-enopyranosides. Conversion of 6-O-acetyl-5-enopyranosides into the corresponding substituted cyclohexanones (Ferrier-II rearrangement) was found to proceed efficiently with a catalytic amount of palladium dichloride. Stereoselective reduction of β-hydroxy ketones obtained provided the precursors to all inositol diastereoisomers in good to excellent yields and with high stereoselectivities. Good accessibility of these enantiomerically pure inositol diastereoisomers results in the efficient syntheses of D-myo-inositol 1,4,5-trisphosphate and D-myo-inositol 1,3,4,5-tetrakisphosphate.
Novel synthesis of enantiomerically pure natural inositols and their diastereomers
Takahashi, Hideyo,Kittaka, Hisae,Ikegami, Shiro
, p. 9707 - 9710 (2007/10/03)
A novel synthesis of all stereoisomers of natural inositols has been developed. The key strategy is the stereoselective reduction of substituted β-hydroxy cyclohexanones which are prepared from a variety of 6-O-acetyl 5- enopyranosides via Ferrier-II reaction catalyzed by palladium chloride. The utility of this approach is demonstrated by the synthesis of D-myo-inositol 1,4,5-tris(phosphate)(IP3).
Transformation of cyclohexene to enantiopure cyclitols mediated by sequential oxyselenenylation with (S,S)-hydrobenzoin: Synthesis of D-chiro-inositol and muco-quercitol
Kim, Kwan Soo,Park, Jong H.,Moon, Hoi Kyung,Yi, Hann
, p. 1945 - 1946 (2007/10/03)
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.
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
Hudlicky, Tomas,Mandel, Martin,Rouden, Jacques,Lee, Robert S.,Bachmann, Bryan,et al.
, p. 1553 - 1568 (2007/10/02)
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.
General Synthesis of Inositols by Hydrolysis of Conduritol Epoxides Obtained Biocatalytically from Halogenobenzenes: (+)-D-chiro-Inositol, allo-Inositol, muco-Inositol and neo-Inositol
Mandel, Martin,Hudlicky, Thomas
, p. 741 - 744 (2007/10/02)
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).
GLYCOSYL-INOSITOL DERIVATIVES III. SYNTHESIS OF HEXOSAMINE-INOSITOL-PHOSPHATES RELATED TO PUTATIVE INSULIN MEDIATORS
Berlin, William K.,Zhang, Wen-Sheng,Shen, T. Y.
, p. 1 - 20 (2007/10/02)
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.
NOVEL BIOSYNTHESIS OF D-PINITOL IN SIMMONDSIA CHINENSIS
Dittrich, Peter,Korak, Andrea
, p. 65 - 66 (2007/10/02)
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.
