@article { ISI:000253515100019, title = {Inositol derived crown ethers: effect of auxiliary protecting groups and the relative orientation of crown ether oxygen atoms on their metal ion binding ability}, journal = {Tetrahedron}, volume = {64}, number = {9}, year = {2008}, month = {FEB}, pages = {2160-2171}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

The binding constants of crown ethers prepared from tetra-O-substituted myo- and scyllo-inositol derivatives and 2-O-substituted myo- and scyllo-inositol-1,3,5-orthoformates, with metal picrates show that the O-substituents and the relative orientation of the crown ether oxygen atoms contribute significantly to the binding of crown ethers with metal ions. In particular, the binding efficiency of myo-inositol derived crown ethers to silver and potassium ions could be enhanced by introducing benzyl ethers in the inositol ring. Hence binding efficacy and selectivity of metal ions to inositol derived crown ethers can be tuned by varying substituents on the myo-inositol ring and/or the relative orientation of crown ether oxygen atoms. (C) 2007 Elsevier Ltd. All rights reserved.

}, keywords = {crown ether, Cyclitol, Inositol, ligand, metal complex, supramolecule}, issn = {0040-4020}, doi = {10.1016/j.tet.2007.12.034}, author = {Dixit, Shailesh S. and Shashidhar, Mysore S.} } @article { ISI:000264206200011, title = {Regioselective O-acylation of myo-inositol 1,3,5-orthoesters: dependence of regioselectivity on the stoichiometry of the base}, journal = {Tetrahedron}, volume = {65}, number = {13}, year = {2009}, month = {MAR}, pages = {2703-2710}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

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.

}, keywords = {Acylation, Cyclitol, Inositol, Orthoester, Regioselectivity, transesterification}, issn = {0040-4020}, doi = {10.1016/j.tet.2009.01.060}, author = {Sureshan, Kana M. and Devaraj, Subramanian and Shashidhar, Mysore S.} } @article { ISI:000267728000002, title = {Relative reactivity of hydroxyl groups in inositol derivatives: role of metal ion chelation}, journal = {Carbohydrate Research}, volume = {344}, number = {10}, year = {2009}, month = {JUL}, pages = {1159-1166}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

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.

}, keywords = {Carbohydrate, Chelation, Cyclitol, Inositol, Protecting group}, issn = {0008-6215}, doi = {10.1016/j.carres.2009.04.007}, author = {Devaraj, Subramanian and Jagdhane, Rajendra C. and Shashidhar, Mysore S.} } @article { ISI:000295564100011, title = {Formal synthesis of valiolamine from myo-inositol}, journal = {Tetrahedron}, volume = {67}, number = {41}, year = {2011}, month = {OCT}, pages = {7963-7970}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

An efficient formal synthesis of racemic valiolamine starting from readily available myo-inositol is reported. In all the synthetic steps only one regioisomer is formed, which circumvents laborious purification of products. Regioselective benzylation of myo-inositol orthoformate, super-hydride mediated deoxygenation of a cyclitol derivative and stereoselective addition of dichloromethyllithium to an inosose are the key reactions in the synthesis. (C) 2011 Elsevier Ltd. All rights reserved.

}, keywords = {Amino sugar, Carbohydrate, Cyclitol, Inositol, Natural product, Valiolamine}, issn = {0040-4020}, doi = {10.1016/j.tet.2011.08.027}, author = {Jagdhane, Rajendra C. and Shashidhar, Mysore S.} } @article { ISI:000292472400016, title = {Protecting group directed stereoselective reduction of an epi-inosose: efficient synthesis of epi-inositol}, journal = {Tetrahedron Letters}, volume = {52}, number = {29}, year = {2011}, month = {JUL}, pages = {3756-3758}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A facile and high yielding synthesis of epi-inositol via stereoselective reduction of a pentaprotected epi-inosose is reported. Extent of stereoselectivity during the hydride reduction appears to depend on the ability of the substrate to complex with metal ions in the reducing agent. (C) 2011 Elsevier Ltd. All rights reserved.

}, keywords = {Cyclitol, Inositol, Polyol, reduction, Stereoselective}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2011.05.051}, author = {Patil, Madhuri T. and Krishnaswamy, Shobhana and Sarmah, Manash P. and Shashidhar, Mysore S.} } @article { ISI:000310402400032, title = {Elaboration of the ether cleaving ability and selectivity of the classical pearlman{\textquoteright}s catalyst [Pd(OH)(2)/C]: concise synthesis of a precursor for a myo-inositol pyrophosphate}, journal = {Tetrahedron}, volume = {68}, number = {47}, year = {2012}, month = {NOV}, pages = {9769-9776}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

The cleavage of propargyl, allyl, benzyl, and PMB ethers by Pd(OH)(2)/C can be tuned in that order, by varying the reaction conditions. Other moieties such as C-C double bonds, esters, trityl ether, p-bromo and p-nitrobenzyl ethers are stable to these reaction conditions. Cleavage of allyl ethers can be made catalytic by using 1:1 mixture of Pd(OH)(2)/C and Pd/C. The synthetic potential of the selective ether cleaving ability of Pd(OH)(2)/C, essentially under neutral conditions, has been demonstrated by an efficient synthesis of a precursor for the preparation of an inositol pyrophosphate derivative. (C) 2012 Elsevier Ltd. All rights reserved.

}, keywords = {Cyclitol, Ether cleavage, Inositol, Palladium, Protecting group}, issn = {0040-4020}, doi = {10.1016/j.tet.2012.09.016}, author = {Mart, Alson and Shashidhar, Mysore S.} } @article { ISI:000319647600012, title = {Orientation of the beta-hydroxyl group controls the diastereoselectivity during the hydride reduction and grignard reaction of inososes}, journal = {Tetrahedron}, volume = {69}, number = {25}, year = {2013}, month = {JUN}, pages = {5144-5151}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A comparison of the results of the Grignard reaction and the hydride reduction of the carbonyl group of epi- and scyllo-inososes reveals that the extent of diastereoselectivity of these reactions is decided by the orientation of the beta-hydroxyl group (or its derivative). Presence of an axial beta-hydroxyl group generally results in the formation of relatively larger amount of the axial alcohol as a result of the reduction of the carbonyl group. The possible reasons for the observed differences in diastereoselectivity between the reactions of these isomeric epi- and scyllo-inososes have been discussed. The sequence of reactions reported here provides convenient access to C-allcylated inositols, such as iso-laminitol and iso-mytilitol as well as 2-O-methyl epi-inositol, an epimer of the naturally occurring ononitol. (C) 2013 Elsevier Ltd. All rights reserved.

}, keywords = {Cyclitol, diastereoselectivity, Grignard, Inositol, Nucleophile, reduction}, issn = {0040-4020}, doi = {10.1016/j.tet.2013.04.081}, author = {Jagdhane, Rajendra C. and Patil, Madhuri T. and Krishnaswamy, Shobhana and Shashidhar, Mysore S.} } @article { ISI:000344880800003, title = {Myo-Inositol 1,3-acetals as early intermediates during the synthesis of cyclitol derivatives}, journal = {Carbohydrate Research}, volume = {399}, year = {2014}, month = {NOV}, pages = {8-14}, publisher = {ELSEVIER SCI LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLAND}, abstract = {

Synthetic sequences starting from commercially available myo-inositol necessarily involve protection-deprotection strategies of its six hydroxyl groups. Several strategies have been developed/attempted over the last several decades leading to the synthesis of naturally occurring phosphoinositols, their analogs, and cyclitol derivatives. Of late, myo-inositol 1,3-acetals, which can be obtained by the reductive cleavage of myo-inositol orthoesters have emerged as early intermediates for the synthesis of phosphorylated and other inositol derivatives. This mini-review is an attempt to illustrate the economy and convenience of using myo-inositol 1,3-acetals as early intermediates during syntheses from myo-inositol. (C) 2014 Elsevier Ltd. All rights reserved.

}, keywords = {Acetal, Cyclitol, Inositol, Protecting group, Signal transduction}, issn = {0008-6215}, doi = {10.1016/j.carres.2014.08.010}, author = {Gurale, Bharat P. and Sardessai, Richa S. and Shashidhar, Mysore S.} } @article {49699, title = {Desymmetrization of myo-inositol}, journal = {Carbohydrate Research}, volume = {553}, year = {2025}, month = {JUL}, pages = {109505}, type = {Article}, abstract = {

Chemistry and biology of phosphoinositols have been intensely investigated areas of research over the last 4-5 decades due to their involvement in cellular signal transduction pathways. Efficient laboratory synthesis of enantiomeric derivatives of inositols was a central issue since they were required for the delineation of the myo-inositol cycle as well as for the total synthesis of polyol based natural products and their derivatives. This essentially meant the development of competent methods for the desymmetrization of myo-inositol leading to the preparation of enantiomeric O-substituted derivatives of myo-inositol. This was approached by: the classical resolution methods involving separable diastereomers, the chiral pool synthesis, enzyme catalysis, asymmetric catalysis and preferential crystallization of enantiomers in a racemic conglomerate. This review summarizes results obtained in author{\textquoteright}s laboratory, as well as those reported in the literature on attempts at desymmetrization of myo-inositol.

}, keywords = {Conglomerate, Crystallization, Cyclitol, Enantiomers, Inositol, Lipid}, issn = {0008-6215}, doi = {10.1016/j.carres.2025.109505}, author = {Patil, Nivedita T. and Patil, Madhuri T. and Gonnade, Rajesh G. and Shashidhar, Mysore S.} }