01778nas a2200241   4500008004100000022001400041245008200055210006900137260010600206300001400312490000700326520092900333653001401262653001801276653001801294653000901312653001301321100002301334700002701357700001701384700002701401856010801428       2011                        eng d  a0040-402000aThermal epimerization of inositol 1,3-benzylidene acetals in the molten state0 aThermal epimerization of inositol 13benzylidene acetals in the m  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcSEP  a7280-72880 v673 a<p>1,3-O-Benzylidene-2,4,5,6-tetra-O-substituted-myo-inositol derivatives obtained by the DIBAL-H reduction of the corresponding myo-inositol 1,3,5-orthobenzoate derivatives undergo epimerization at the acetal carbon on heating, in the molten state, just above their melting point. The same epimerization reaction does not proceed either in the crystalline state or in solution. DFT calculations suggest that the epimeric acetal obtained by this thermal process is relatively more stable than the starting acetal. Either of these acetals could not be obtained by the reaction of the corresponding inositol derived diol with benzaldehyde. These observations constitute a novel reaction solely in the molten state, which are rarely encountered in the literature. X-ray crystal structures of the epimeric acetals as well as their radical deoxygenation reaction are also reported. (C) 2011 Elsevier Ltd. All rights reserved.</p>10acyclitols10aDeoxygenation10aEpimerization10aMelt10aXanthate1 aGurale, Bharat, P.1 aKrishnaswamy, Shobhana1 aVanka, Kumar1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/thermal-epimerization-inositol-13-benzylidene-acetals-molten-state-001936nas a2200241   4500008004100000022001400041245017900055210006900234260007500303300001600378490000700394520095700401653002401358653001401382653001401396653003001410653002601440100002301466700002701489700002401516700002701540856012701567       2015                        eng d  a0947-653900aIntramolecular cyclization of carbonate and thiocarbonate derivatives of myo-inositol in the solid state: implications for acyl group transfer reactions in molecular crystals0 aIntramolecular cyclization of carbonate and thiocarbonate deriva  aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcSEP  a13676-136820 v213 a<p>Racemic 4-O-phenoxycarbonyl and 4-O-phenoxythiocarbonyl derivatives of myo-inositol orthoformate undergo thermal intramolecular cyclization in the solid state to yield the corresponding 4,6-bridged carbonates and thiocarbonates, respectively. The thermal cyclization also occurs in the solution and molten states, but less efficiently, suggesting that these cyclization reactions are aided by molecular pre-organization, although not strictly topochemically controlled. Crystal structures of two carbonates and a thiocarbonate clearly revealed that the relative orientation of the electrophile and the nucleophile in the crystal lattice facilitates the intramolecular cyclization reaction and forbids the intermolecular reaction. The correlation observed between the chemical reactivity and the non-covalent interactions in the crystal of the reactants provides a way to estimate the chemical stability of analogous molecules in the solid state.</p>10acrystal engineering10acyclitols10ainositols10anucleophilic substitution10asolid-phase synthesis1 aTamboli, Majid, I.1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aKrishnaswamy, Shobhana  uhttps://library.ncl.res.in/content/intramolecular-cyclization-carbonate-and-thiocarbonate-derivatives-myo-inositol-solid-0