@article { ISI:000262301900031,
	title = {Enhancing intermolecular benzoyl-transfer reactivity in crystals by growing a {\textquoteleft}{\textquoteleft}reactive{\textquoteright}{\textquoteright} metastable polymorph by using a chiral additive},
	journal = {Chemistry-A European Journal},
	volume = {15},
	number = {1},
	year = {2009},
	month = {NOV},
	pages = {261-269},
	publisher = {WILEY-V C H VERLAG GMBH},
	address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY},
	abstract = {<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>},
	keywords = {Acylation, carbohydrates, Crystal growth, cyclitols, solid-state reactions},
	issn = {0947-6539},
	doi = {10.1002/chem.200801484},
	author = {Murali, Chebrolu and Shashidhar, Mysore S. and Gonnade, Rajesh G. and Bhadbhade, Mohan M.}
}
@article { ISI:000361190200026,
	title = {Intramolecular cyclization of carbonate and thiocarbonate derivatives of myo-inositol in the solid state: implications for acyl group transfer reactions in molecular crystals},
	journal = {Chemistry-A European Journal},
	volume = {21},
	number = {39},
	year = {2015},
	month = {SEP},
	pages = {13676-13682},
	publisher = {WILEY-V C H VERLAG GMBH},
	address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY},
	abstract = {<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>},
	keywords = {crystal engineering, cyclitols, inositols, nucleophilic substitution, solid-phase synthesis},
	issn = {0947-6539},
	doi = {10.1002/chem.201501480},
	author = {Tamboli, Majid I. and Shashidhar, Mysore S. and Gonnade, Rajesh G. and Krishnaswamy, Shobhana}
}
