01549nas a2200169   4500008004100000022001400041245015200055210006900207260010600276300001200382490000700394520077900401100002501180700002301205700002401228856012701252       2005                        eng d  a0040-402000aChelation controlled regiospecific O-substitution of myo-inositol orthoesters: convenient access to orthogonally protected myo-inositol derivatives0 aChelation controlled regiospecific Osubstitution of myoinositol   aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcJAN  a529-5360 v613 a<p>A general method for the completely regioselective protection of the three secondary hydroxyl groups of orthoester derivatives of myo-mositol, utilizing the subtle differences in reactivity exhibited by its alkali metal alkoxides due to differences in their ability to form chelates, is described. This method provides convenient access to orthogonally protected myo-inositol derivatives. A comparison of the methylation of racemic 4-0-trityl-myo-inositol 1,3,5-orthoformate in the presence of sodium or lithium ions showed that stabilization of the C4-alkoxide by chelation with lithium overrides steric hindrance offered by the C6-axial substituent in deciding the regioselectivity during the nucleophilic O-substitution. (C) 2004 Elsevier Ltd. All rights reserved.</p>1 aDevaraj, Subramanian1 aShashidhar, M., S.1 aDixit, Shailesh, S.  uhttps://library.ncl.res.in/content/chelation-controlled-regiospecific-o-substitution-myo-inositol-orthoesters-convenient-000873nas a2200181   4500008004100000022001400041245021600055210006900271260008100340300001400421490000700435100002400442700002500466700002400491700002500515700002300540856012800563       2005                        eng d  a0108-270100aO-H center dot center dot center dot O-bridged dimers linked via C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions in 4,6-di-O-benzyl-myo-inositol 1,3,5-orthoformate0 aOH center dot center dot center dot Obridged dimers linked via C  a9600 GARSINGTON RD, OXFORD OX4 2DQ, OXON, ENGLANDbBLACKWELL PUBLISHINGcNOV  aO628-O6300 v611 aManoj, Kochunnoonny1 aDevaraj, Subramanian1 aGonnade, Rajesh, G.1 aBhadbhade, Mohan, M.1 aShashidhar, M., S.  uhttps://library.ncl.res.in/content/o-h-center-dot-center-dot-center-dot-o-bridged-dimers-linked-c-h-center-dot-center-dot-001734nas a2200241   4500008004100000022001400041245018600055210006900241260010600310300001400416490000700430520077100437653001601208653001301224653001301237653001101250653001201261653001801273100002401291700002301315700002501338856012901363       2006                        eng d  a0040-402000aCyclitol based metal complexing agents. preference for the extraction of lithium by myo-inositol based crown-4-ethers depends on the relative orientation of crown ether oxygen atoms0 aCyclitol based metal complexing agents preference for the extrac  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcMAY  a4360-43630 v623 a<p>myo-Inositol derived crown-4-ethers in which two of the oxygen atoms in the crown ether moiety have different relative orientations were prepared. Metal picrate binding studies revealed that the crown ether having 1,3-diaxial orientation shows the highest selectivity for binding to lithium although the crown ether having 1,2-diequatorial orientation exhibited the highest binding constant for lithium picrate. These results suggest that relative binding affinity of metal ions to crown ethers can be tuned by varying the relative orientation of crown ether oxygen atoms. The relevance of these results to the previously observed regioselectivity during the O-substitution of myo-inositol orthoesters is discussed. (c) 2606 Elsevier Ltd. All rights reserved.</p>10acrown ether10aCyclitol10aInositol10aligand10alithium10ametal complex1 aDixit, Shailesh, S.1 aShashidhar, M., S.1 aDevaraj, Subramanian  uhttps://library.ncl.res.in/content/cyclitol-based-metal-complexing-agents-preference-extraction-lithium-myo-inositol-based-001817nas a2200241   4500008004100000022001400041245013000055210006900185260010600254300001400360490000700374520089400381653001401275653001301289653001301302653001501315653002101330653002401351100002301375700002501398700002701423856012501450       2009                        eng d  a0040-402000aRegioselective O-acylation of myo-inositol 1,3,5-orthoesters: dependence of regioselectivity on the stoichiometry of the base0 aRegioselective Oacylation of myoinositol 135orthoesters dependen  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcMAR  a2703-27100 v653 a<p>A metal mediated unusual 1-3 acyl migration from C4-O to C2-OH of myo-inositol 1,3,5-orthoformate was observed during the alkylation of racemic 4-O-benzoyl-myo-inositol 1,3,5-orthoformate. This has been exploited for the selective esterification of either the C4(6)-OH or the C2-OH of myo-inositol by varying the amount of the base used. While the use of 1 equiv of the base (sodium hydride or potassium tert-butoxide) for the acylation of myo-inositol orthoesters gives the corresponding C4-ester exclusively, the use of two or more equivalents of base for the same reaction gives the C2-ester exclusively. The relatively higher stability of the alkoxide of racemic 2-O-acyl-myo-inositol 1,3,5-orthoester as compared to the alkoxide of 4-O-acyl-myo-inositol 1,3,5-orthoester is suggested to be responsible for the observed isomerization. (c) 2009 Elsevier Ltd. All rights reserved.</p>10aAcylation10aCyclitol10aInositol10aOrthoester10aRegioselectivity10atransesterification1 aSureshan, Kana, M.1 aDevaraj, Subramanian1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/regioselective-o-acylation-myo-inositol-135-orthoesters-dependence-regioselectivity-001863nas a2200229   4500008004100000022001400041245009600055210006900151260009900220300001400319490000800333520101200341653001701353653001401370653001301384653001301397653002101410100002501431700002701456700002701483856012301510       2009                        eng d  a0008-621500aRelative reactivity of hydroxyl groups in inositol derivatives: role of metal ion chelation0 aRelative reactivity of hydroxyl groups in inositol derivatives r  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLANDbELSEVIER SCI LTDcJUL  a1159-11660 v3443 a<p>O-Alkylation of myo-inositol derivatives containing more than one hydroxyl group via their alkali metal alkoxides (sodium or lithium) preferentially occurs at a hydroxyl group having a vicinal cis-oxygen atom. In general the observed selectivity is relatively higher for lithium alkoxides than for the corresponding sodium alkoxide. The observed regioselectivity is also dependent on other factors such as the solvent and reaction temperature. A perusal of the results presented in this article as well as those available in the literature suggests that chelation of metal ions by inositol derivatives plays a significant role in the observed regioselectivity. Steric factors associated with the axial or equatorial disposition of the reacting hydroxyl groups do not contribute much to the outcome of these O-alkylation reactions. These results could serve as guidelines in planning synthetic strategies involving other carbohydrates and their derivatives. (C) 2009 Elsevier Ltd. All rights reserved.</p>10aCarbohydrate10aChelation10aCyclitol10aInositol10aProtecting group1 aDevaraj, Subramanian1 aJagdhane, Rajendra, C.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/relative-reactivity-hydroxyl-groups-inositol-derivatives-role-metal-ion-chelation-0