02131nas a2200253 4500008004100000022001400041245017900055210006900234260007300303300001400376490000800390520117100398653000801569653001301577653001501590653001801605653002201623653000801645100002101653700002701674700002401701700002501725856012701750 2007 eng d a0927-775700aInvestigating organization of molecules that facilitates intermolecular acyl transfer in crystals: reactivity and x-ray structures of O-benzoyl-myo-inositol 1,3,5-orthoesters0 aInvestigating organization of molecules that facilitates intermo aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB a1153-11590 v2933 a

{Crystal structure analysis of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthobenzoate reveals helical organization of the molecules, remarkably similar to that observed earlier in crystals of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthoformate. Both these dibenzoates are isostructural despite the bulkier phenyl substituent in place of hydrogen. The latter compound shows highly facile intermolecular benzoyl transfer reactivity in its crystals and as anticipated from the crystal structure, the orthobenzoate indeed exhibits facile benzoyl transfer reactivity in its crystals. 2-O-Benzoyl-myo-inositol 1,3,5-orthoformate and the corresponding orthobenzoate also undergo transesterification in their crystals, but the specificity of acyl transfer is very low, and the reaction yields a mixture of products. The parameters of helical molecular assembly that facilitates acyl transfer in crystals have been investigated. A comparison of the molecular assemblies and lattice interactions in crystals of all the four compounds with the observed reactivity patterns show that facile acyl transfer reaction is brought about by a modular ``reaction tunnel''

10aAOT10aCdS-Ag2S10acore-shell10aNanoparticles10aw/o microemulsion10aXPS1 aMurali, Chebrolu1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aBhadbhade, Mohan, M. uhttp://library.ncl.res.in/content/investigating-organization-molecules-facilitates-intermolecular-acyl-transfer-crystals-001711nas a2200229 4500008004100000022001400041245016500055210006900220260010600289300001400395490000700409520079500416653001601211653001301227653001301240653001101253653001801264653001801282100002401300700002701324856013001351 2008 eng d a0040-402000aInositol derived crown ethers: effect of auxiliary protecting groups and the relative orientation of crown ether oxygen atoms on their metal ion binding ability0 aInositol derived crown ethers effect of auxiliary protecting gro aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcFEB a2160-21710 v643 a

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.

10acrown ether10aCyclitol10aInositol10aligand10ametal complex10asupramolecule1 aDixit, Shailesh, S.1 aShashidhar, Mysore, S. uhttp://library.ncl.res.in/content/inositol-derived-crown-ethers-effect-auxiliary-protecting-groups-and-relative-orientation-001860nas a2200181 4500008004100000022001400041245022400055210006900279260011000348300001400458490000700472520097200479100002401451700002401475700002501499700002701524856012701551 2009 eng d a1466-803300aIsostructural molecular strings linked via conserved dipolar (ether) O center dot center dot center dot C=O short contacts in conformational polymorphs of racemic 2,4-di-O-acetyl-6-O-tosyl-myo-inositol 1,3,5-orthoesters0 aIsostructural molecular strings linked via conserved dipolar eth aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a1022-10290 v113 a

Conformational dimorphs of racemic 2,4-di-O-acetyl-6-O-tosyl-myo-inositol 1,3,5-orthoformate and its orthoacetate analogue were characterized using single crystal X-ray diffraction, thermal analysis and hot-stage microscopy techniques. In these polymorphs, the tosyl group adopted different conformations due to the rotation about the O-S bond. A significant variation in the torsion angle for the tosyl group (similar to 56 degrees) was observed for Form II crystal of the orthoformate derivative, which exhibited an intramolecular dipolar S=O center dot center dot center dot C=O (sulfonyl-carbonyl) short contact. An interesting feature in all conformational polymorphs is the formation of an isostructural string (despite the differences in the orientation of the tosyl group) linked via dipolar (ether) O center dot center dot center dot C=O contacts, which is further stitched by other weak interactions to form different layers in their crystal lattice.

1 aManoj, Kochunnoonny1 aGonnade, Rajesh, G.1 aBhadbhade, Mohan, M.1 aShashidhar, Mysore, S. uhttp://library.ncl.res.in/content/isostructural-molecular-strings-linked-conserved-dipolar-ether-o-center-dot-center-dot-001738nas a2200241 4500008004100000022001400041245011700055210006900172260007700241300001200318520085800330653001401188653001801202653001401220653001301234653002201247653001301269653001301282100002101295700002301316700002701339856013001366 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

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.

10acyclitols10aDeoxygenation10aInosamine10aInositol10aRadical reactions10aRadicals10aXanthate1 aMurali, Chebrolu1 aGurale, Bharat, P.1 aShashidhar, Mysore, S. uhttp://library.ncl.res.in/content/intramolecular-hydrogen-abstraction-radicals-derived-inositol-13-acetals-efficient-access-002045nas a2200169 4500008004100000022001400041245018900055210006900244260011000313300001400423490000700437520122600444100002701670700002701697700002501724856012601749 2011 eng d a1466-803300aIntermolecular benzoyl group transfer reactivity in crystals of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthobenzoate: controlling reactivity by solvate (pseudopolymorph) formation0 aIntermolecular benzoyl group transfer reactivity in crystals of  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAY a3258-32640 v133 a

Racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthobenzoate (rac-3), which usually crystallizes in a monoclinic lattice (Form I, P2(1)/c) from common organic solvents, when crystallized from 2-propanol yielded concomitantly, thin whisker like crystals (Form II, triclinic, P (1) over bar) with inclusion of 2-propanol and water molecules, along with the Form I crystals. Thin fibre-like crystals were also obtained on crystallization from toluene, with inclusion of toluene and water in the crystal lattice (Form III). The Form II and Form III crystals could be converted into the Form I crystals thermally via melt crystallization. Form I crystals exhibit a facile transesterification reaction, but the solvated crystals are unreactive under the same conditions until their transformation to the reactive form. The reactivity patterns of the Form I and Form II crystals correlate well with the molecular organization in them. Since reactivity of the crystals of rac-3 depends on the solvent and the method of crystallization, and the thermal transition of one crystal form to the other, these phase changes can be used as a switch to control the benzoyl transfer reactivity of the constituent molecules in crystals.

1 aKrishnaswamy, Shobhana1 aShashidhar, Mysore, S.1 aBhadbhade, Mohan, M. uhttp://library.ncl.res.in/content/intermolecular-benzoyl-group-transfer-reactivity-crystals-racemic-26-di-o-benzoyl-myo-002006nas a2200241 4500008004100000022001400041245014900055210006900204260007700273300001600350490000700366520105300373653001401426653002101440653003201461653002601493653002201519100002301541700002701564700002401591700002701615856012201642 2013 eng d a0947-653900aIdentification of molecular crystals capable of undergoing an acyl-transfer reaction based on intermolecular interactions in the crystal lattice0 aIdentification of molecular crystals capable of undergoing an ac aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcSEP a12867-128740 v193 a

Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1)the favorable geometry of the nucleophile (OH) and the electrophile (CO) and 2)the molecular assembly, reinforced by CH interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity.

10aAcylation10adomino reactions10aintermolecular interactions10asolid-state reactions10aX-ray diffraction1 aTamboli, Majid, I.1 aKrishnaswamy, Shobhana1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S. uhttp://library.ncl.res.in/content/identification-molecular-crystals-capable-undergoing-acyl-transfer-reaction-based-001935nas a2200241 4500008004100000022001400041245017900055210006900234260007500303300001600378490000700394520095700401653002401358653001401382653001401396653003001410653002601440100002301466700002701489700002401516700002701540856012601567 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

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.

10acrystal engineering10acyclitols10ainositols10anucleophilic substitution10asolid-phase synthesis1 aTamboli, Majid, I.1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aKrishnaswamy, Shobhana uhttp://library.ncl.res.in/content/intramolecular-cyclization-carbonate-and-thiocarbonate-derivatives-myo-inositol-solid-001304nas a2200169 4500008004100000245007900041210006900120260000800189300001000197490000800207520071400215100002300929700002700952700002500979700002401004856010601028 2018 eng d00aInositol to aromatics -benzene free synthesis of poly oxygenated aromatics0 aInositol to aromatics benzene free synthesis of poly oxygenated  cMAY a38-440 v4613 aA method for the preparation of benzene derivatives from myo-inositol, an abundantly available phyto chemical is described. 1,3-Bridged acetals of inososes undergo step-wise elimination leading to the formation of polyoxygenated benzene derivatives. This aromatization reaction proceeds through the intermediacy of a beta-alkoxyenone, which could be isolated. This sequence of reactions starting from myoinositol, provides a novel route for the preparation of polyoxygenated benzene derivatives including polyoxygenated biphenyl. This scheme of synthesis demonstrates the potential of myo-inositol as a sustainable non-petrochemical resource for aromatic compounds. (C) 2018 Elsevier Ltd. All rights reserved.1 aGurale, Bharat, P.1 aShashidhar, Mysore, S.1 aSardessai, Richa, S.1 aGonnade, Rajesh, G. uhttp://library.ncl.res.in/content/inositol-aromatics-benzene-free-synthesis-poly-oxygenated-aromatics09145nas a2200145 4500008004100000245006700041210006400108260000800172300001200180490000700192520865000199100002708849700002708876856009608903 2019 eng d00a Intermolecular acyl-transfer reactions in molecular crystals 0 aIntermolecular acyltransfer reactions in molecular crystals cFEB a437-4460 v523 a

CONSPECTUS: It is far more difficult to recognize and predict the chemical reactions that a molecule of an organic compound can undergo in crystalline (solid) state as compared to the solution state (the "organic functional group" approach), since the published data on solid-state structure reactivity investigations and correlations are scant. The discovery of the first intermolecular acyl-transfer reaction in molecular crystals of racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoformate (DiBz) during our attempts to develop methods for the synthesis of phosphoinositols, motivated us to find other molecular crystals capable of supporting similar reactions. Small changes to the molecular structure of DiBz yielded analogues with different crystal structures which showed varying degrees of acyl transfer reactivity as compared to the crystals of DiBz. A systematic investigation of the structures, polymorphism, cocrystallization behavior, and the corresponding reactivity of these crystals allowed us to correlate the acyl transfer reactivity with their structures and inherent noncovalent interactions and provided crucial insights into the mechanism of these reactions. Polymorphs or cocrystals of these compounds exhibited dissimilar reactivities due to differences in the molecular conformation and/or arrangements in their crystals. The knowledge of phase transitions between polymorphs enabled us to control and tune the reactivity in the solid state. We could identify three conditions essential for intermolecular acyl transfer: (i) favorable relative geometry of the electrophile (ester C=O) and the nucleophile (OH), (ii) noncovalent interactions (C-H center dot center dot center dot pi) between the reacting molecules which help in maintaining the facility and specificity of the reaction, and (iii) the presence of channels in the lattice which enable propagation of the reaction in the crystal. Based on this supramolecular structure reactivity correlation, we identified other molecular crystals (composed of molecules of widely different molecular structure from that of DiBz) from a survey of the Cambridge Structural Database (CSD) and predicted their acyl transfer reactivity. The increased availability of user-friendly modern X-ray diffractometers and related software has enabled efficient collection, analysis and interpretation of single crystal X-ray diffraction data, essential for such studies. The rapidly expanding CSD facilitates the identification of crystals with similar structures and reactivity patterns. In a wider perspective, facile reactions in molecular crystals fascinate chemists because these reactions usually exhibit unique product selectivity and have the potential to be developed as sustainable green reactions. We are optimistic that similar approaches for the study of other group transfer reactions in molecular crystals would augment and widen the scope of chemical reactions in molecular crystals in particular and the solid state in general. The ability to predict the reactivity of molecules in their crystals could find applications in organic synthesis, material science and industry. Realization of the involvement of inositol derivatives in cellular processes led to the discovery of cellular signal transduction mechanisms. The ability of inositol derivatives to support facile acyl-transfer reactions in the crystalline state might well have opened a new avenue for research in the area of organic solid-state reactions.

1 aShashidhar, Mysore, S.1 aKrishnaswamy, Shobhana uhttp://library.ncl.res.in/content/intermolecular-acyl-transfer-reactions-molecular-crystals