02007nas a2200241   4500008004100000022001400041245014900055210006900204260007700273300001600350490000700366520105300373653001401426653002101440653003201461653002601493653002201519100002301541700002701564700002401591700002701615856012301642       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<p>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.</p>10aAcylation10adomino reactions10aintermolecular interactions10asolid-state reactions10aX-ray diffraction1 aTamboli, Majid, I.1 aKrishnaswamy, Shobhana1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/identification-molecular-crystals-capable-undergoing-acyl-transfer-reaction-based-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