01739nas 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-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-001115nas a2200169   4500008004100000022001400041245011600055210006900171260007600240300001400316490000700330520040200337100002300739700002400762700002700786856013200813       2012                        eng d  a0108-270100aChiral crystals from an achiral molecule: 4,6-di-O-benzyl-1,3-O-benzylidene-2-O-(4-methoxybenzyl)-myo-5-inosose0 aChiral crystals from an achiral molecule 46diObenzyl13Obenzylide  aCOMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USAbWILEY-BLACKWELLcMAY  aO183-O1870 v683 a<p>The title achiral compound, C35H34O7, crystallizes in the chiral monoclinic space group P21. The molecules are densely packed to form a helical assembly along the crystallographic twofold screw axis via CH...O and CH...p interactions. Interestingly, the unit-translated helical chains are loosely connected via a rather uncommon edge-to-edge PhH...HPh short contact (H...H = 2.33 angstrom).</p>1 aGurale, Bharat, P.1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/chiral-crystals-achiral-molecule-46-di-o-benzyl-13-o-benzylidene-2-o-4-methoxybenzyl-myo-5-001868nas a2200241   4500008004100000022001400041245012500055210006900180260009900249300001000348490000800358520098600366653001801352653000801370653001301378653001401391653001201405653001301417100002301430700001701453700002701470856012901497       2012                        eng d  a0008-621500aRadical mediated deoxygenation of inositol benzylidene acetals: conformational analysis, DFT calculations, and mechanism0 aRadical mediated deoxygenation of inositol benzylidene acetals c  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLANDbELSEVIER SCI LTDcAPR  a26-340 v3513 a<p>Xanthates of 1,3-benzylidene acetal derivatives of myo- and neo-inositols undergo dideoxygenation under Barton-McCombie conditions, as a result of intramolecular abstraction of the benzylidene acetal hydrogen and subsequent cleavage of the acetal ring. Scrutiny of structure of these bicyclic inositol derivatives shows that although the conformation of the two rings can vary depending on the configuration of the inositol ring and the phase in which the molecules are present, both the xanthates lead to the formation of the same dideoxyinositol. DFT calculations on these molecular systems suggest that neo-inositol derivatives undergo conformational change prior to radical formation while myo- inositol derivatives undergo conformational change subsequent to radical formation, during the deoxygenation reaction. A low barrier for intramolecular hydrogen transfer supports the extreme facility of this deoxygenation reaction. (C) 2012 Elsevier Ltd. All rights reserved.</p>10aDeoxygenation10aDFT10aInositol10aMechanism10aRadical10aXanthate1 aGurale, Bharat, P.1 aVanka, Kumar1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/radical-mediated-deoxygenation-inositol-benzylidene-acetals-conformational-analysis-dft-001325nas a2200169   4500008004100000022001400041245010100055210006900156260007100225300001400296490000700310520064700317100002300964700002700987700002401014856011701038       2012                        eng d  a0022-326300aSynthesis of the aminocyclitol units of (-)-hygromycin a and methoxyhygromycin from myo-inositol0 aSynthesis of the aminocyclitol units of hygromycin a and methoxy  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL  a5801-58070 v773 a<p>Concise and efficient syntheses of the aminocyclitol cores of hygromycin A (HMA) and methoxyhygromycin (MHM) have been achieved starting from readily available myo-inositol. Reductive cleavage of myo-inositol orthoformate to the corresponding 1,3-acetal, stereospecific introduction of the amino group via the azide, and resolution of a racemic cyclitol derivative as its diastereomeric mandelate esters are the key steps in the synthesis. Synthesis of the aminocyclitol core of hygromycin A involved chromatography in half of the total number of steps, and the aminocyclitol core of methoxyhygromycin involved only one chromatography.</p>1 aGurale, Bharat, P.1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.  uhttps://library.ncl.res.in/content/synthesis-aminocyclitol-units-hygromycin-and-methoxyhygromycin-myo-inositol-001622nas a2200229   4500008004100000022001400041245009700055210006900152260009900221300000900320490000800329520077500337653001101112653001301123653001301136653002101149653002401170100002301194700002501217700002701242856012301269       2014                        eng d  a0008-621500aMyo-Inositol 1,3-acetals as early intermediates during the synthesis of cyclitol derivatives0 aMyoInositol 13acetals as early intermediates during the synthesi  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, OXON, ENGLANDbELSEVIER SCI LTDcNOV  a8-140 v3993 a<p>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.</p>10aAcetal10aCyclitol10aInositol10aProtecting group10aSignal transduction1 aGurale, Bharat, P.1 aSardessai, Richa, S.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/myo-inositol-13-acetals-early-intermediates-during-synthesis-cyclitol-derivatives-001305nas a2200169   4500008004100000245007900041210006900120260000800189300001000197490000800207520071400215100002300929700002700952700002500979700002401004856010701028       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.  uhttps://library.ncl.res.in/content/inositol-aromatics-benzene-free-synthesis-poly-oxygenated-aromatics