@article { ISI:000227933800013,
	title = {Benzoyl transfer reactivities of racemic 2,4-Di-O-acyl-myo-inosityl 1,3,5-orthoesters in the solid state: molecular packing and intermolecular interactions correlate with the ease of the reaction},
	journal = {Chemistry-A European Journal},
	volume = {11},
	number = {7},
	year = {2005},
	month = {MAR},
	pages = {2103-2110},
	publisher = {WILEY-V C H VERLAG GMBH},
	type = {Article},
	address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY},
	abstract = {<p>Racemic 2,4-di-O-acyl-myoinosityl 1,3,5-orthoesters undergo transesterification catalyzed by sodium carbonate with varying ease of reaction in the solid state; reactions in solution and melt do not show such varied differences. An interesting crystal of a 1:1 molecular complex of highly reactive racemic 2,4-di-O-benzoyl-myo-inosityl 1,3,5-orthoformate and its orthoacetate analogue exhibited better reactivity than the latter component alone. Single-crystal X-ray structures of the reactants have been correlated with the observed differences in the acyl-transfer efficiencies in the solid state. Although each of the derivatives helically self-assembles around the crystallographic 2(1) axis linked through O-(HO)-O-... hydrogen bonding, the pre-organization of the reactive groups (C=O [El] and OH [Nu]), C-(HO)-O-... and the C=H(...)pi interactions are significantly more favourable for the reactive derivatives than the less reactive ones. Bond-length distributions also showed differences; the O-C bond of the axial benzoyl group, which gets cleaved during the reaction, is longer (1.345-1.361 angstrom) relative to the chemically equivalent O-C bond of the equatorial benzoyl group (1.316-1.344 angstrom) in the reactive derivatives. These bond-length differences are not significant in the less reactive derivatives. The overall molecular organization is different too; the strikingly discrete helices, which may be viewed as {\textquoteleft}{\textquoteleft}reaction tunnels{\textquoteright}{\textquoteright} and are held by interhelical interactions, are clearly evident in the reactive derivatives in comparison with the less reactive ones.</p>},
	keywords = {hydrogen bonds, Inositol, solid-state reactions, structure elucidation, transesterification},
	issn = {0947-6539},
	doi = {10.1002/chem.200400851},
	author = {Sarmah, M. P. and Gonnade, Rajesh G. and Shashidhar, M. S. and Bhadbhade, Mohan M.}
}
@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.}
}
