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Intramolecular Cyclization of Carbonate and Thiocarbonate Derivatives of myo ‐Inositol in the Solid State: Implications for Acyl Group Transfer Reactions in Molecular Crystals
Author(s) -
Tamboli Majid I.,
Shashidhar Mysore S.,
Gonnade Rajesh G.,
Krishnaswamy Shobhana
Publication year - 2015
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.201501480
Subject(s) - intramolecular force , chemistry , carbonate , solid state , group (periodic table) , inositol , organic chemistry , medicinal chemistry , polymer chemistry , biochemistry , receptor
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.