02641nas a2200241   4500008004100000022001400041245014300055210006900198260007700267300001200344490000700356520171700363653001402080653001802094653001902112653001402131653002602145100002102171700002702192700002402219700002502243856013102268       2009                        eng d  a0947-653900aEnhancing intermolecular benzoyl-transfer reactivity in crystals by growing a ``reactive'' metastable polymorph by using a chiral additive0 aEnhancing intermolecular benzoyltransfer reactivity in crystals   aPO BOX 10 11 61, D-69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcNOV  a261-2690 v153 a<p>Racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate, which normally crystallizes in a monoclinic form (form I, space group P2(1)/n) could be persuaded to crystallize out as a metastable polymorph (form II, space group C2/c) by using a small amount of either D- or L- 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoformate as an additive in the crystallization medium. The structurally similar enantiomeric additive was chosen by the scrutiny of previous experimental results on the crystallization of racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate. Form II crystals call be thermally transformed to form I crystals at about 145 degrees C. The relative organization of the molecules in these dimorphs vary slightly in terms of the helical assembly of molecules, that is, electrophile (El)center dot center dot center dot nucleophile (Nu) and C-H center dot center dot center dot pi interactions, but these minor variations have a profound effect on the facility and specificity of benzoyl-group-transfer reactivity in the two crystal forms. While form II crystals undergo a clean intermolecular benzoyl-group-transfer reaction, form I crystals are less reactive and undergo non-specific benzoyl-group transfer leading to a Mixture of products. The role played by the additive in fine-tuning small changes that are required in the molecular packing opens up the possibility of creating new polymorphs that show varied physical and chemical properties. Crystals of D-2.6-di-O-benzoyl-myo-inositol-1,3,5-orthoformate (additive) did not show facile benzoyl-group-transfer reactivity (in contrast to the corresponding racemic compound) due to the lack of proper juxtaposition and assembly of molecules.</p>10aAcylation10acarbohydrates10aCrystal growth10acyclitols10asolid-state reactions1 aMurali, Chebrolu1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aBhadbhade, Mohan, M.  uhttps://library.ncl.res.in/content/enhancing-intermolecular-benzoyl-transfer-reactivity-crystals-growing-reactive-metastable-001739nas a2200241   4500008004100000022001400041245011700055210006900172260007700241300001200318520085800330653001401188653001801202653001401220653001301234653002201247653001301269653001301282100002101295700002301316700002701339856013101366       2010                        eng d  a1434-193X00aIntramolecular hydrogen abstraction in radicals derived from inositol 1,3-acetals: efficient access to cyclitols0 aIntramolecular hydrogen abstraction in radicals derived from ino  aPO BOX 10 11 61, D-69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcFEB  a755-7643 a<p>The benzylidene acetals obtained by cleavage of the orthobenzoate moiety in myo-mositol 1,3,5-orthobenzoate were used to prepare mono- as well as di-deoxy inositol derivatives via their xanthates. The dideoxygenation is a result of intramolecular abstraction of the benzylidene acetal hydrogen and subsequent cleavage of the acetal ring. Such a cleavage does not take place in analogous acetals derived from other orthoesters. The 1,3-acetals derived from myoinositol 1,3,5-orthoesters were also used to prepare neo-inositol and isomeric deoxy-amino inositols, Most of the reactions in these synthetic sequences starting from myo-inositol give one product in each step. The results presented here show that myo-inositol 1,3,5-orthobenzoate offers many advantages over other orthoesters for the synthesis of cyclitol derivatives from myo-inositol.</p>10acyclitols10aDeoxygenation10aInosamine10aInositol10aRadical reactions10aRadicals10aXanthate1 aMurali, Chebrolu1 aGurale, Bharat, P.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/intramolecular-hydrogen-abstraction-radicals-derived-inositol-13-acetals-efficient-access-001623nas a2200205   4500008004100000022001400041245013900055210006900194260007600263300001400339520079900353653001501152653001401167653001301181653002201194653002101216100002701237700002701264856012601291       2010                        eng d  a1434-193X00aOrthogonally protected cyclohexanehexols by a ``one reaction - one product'' approach: efficient access to cyclitols and their analogs0 aOrthogonally protected cyclohexanehexols by a one reaction one p  aCOMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USAbWILEY-BLACKWELLcMAY  a2945-29533 a<p>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.</p>10aAlkylation10acyclitols10aInositol10aProtecting groups10aRegioselectivity1 aJagdhane, Rajendra, C.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/orthogonally-protected-cyclohexanehexols-one-reaction-one-product-approach-efficient-001778nas 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