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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
Author(s) -
Sarmah Manash P.,
Gonnade Rajesh G.,
Shashidhar Mysore S.,
Bhadbhade Mohan M.
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400851
Subject(s) - chemistry , reactivity (psychology) , intermolecular force , hydrogen bond , reactive intermediate , transesterification , molecule , solid state , stereochemistry , crystallography , catalysis , medicinal chemistry , organic chemistry , medicine , alternative medicine , pathology
Racemic 2,4‐di‐ O ‐acyl‐ myo ‐inosityl 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 OH⋅⋅⋅O hydrogen bonding, the pre‐organization of the reactive groups (CO [El] and OH [Nu]), CH⋅⋅⋅O and the CH⋅⋅⋅π interactions are significantly more favourable for the reactive derivatives than the less reactive ones. Bond‐length distributions also showed differences; the OC bond of the axial benzoyl group, which gets cleaved during the reaction, is longer (1.345–1.361 Å) relative to the chemically equivalent OC bond of the equatorial benzoyl group (1.316–1.344 Å) 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 “reaction tunnels” and are held by interhelical interactions, are clearly evident in the reactive derivatives in comparison with the less reactive ones.