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Identification of Molecular Crystals Capable of Undergoing an Acyl‐Transfer Reaction Based on Intermolecular Interactions in the Crystal Lattice
Author(s) -
Tamboli Majid I.,
Krishnaswamy Shobhana,
Gonnade Rajesh G.,
Shashidhar Mysore S.
Publication year - 2013
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.201301058
Subject(s) - intermolecular force , reactivity (psychology) , chemistry , nucleophile , crystal (programming language) , electrophile , crystal structure , crystallography , molecule , crystal engineering , diol , organic chemistry , supramolecular chemistry , catalysis , medicine , alternative medicine , pathology , computer science , programming language
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⋅⋅⋅π 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.