Identification of Molecular Crystals Capable of Undergoing an Acyl‐Transfer Reaction Based on Intermolecular Interactions in the Crystal Lattice. Issue 38 (9th August 2013)

• Record Type: Journal Article
• Authors: Tamboli, Majid I.; Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S.
• Is Part Of: Chemistry. Volume 19:Issue 38(2013)
• Page Start: 12867
• Page End: 12874
• Publication Date: 2013-08-09
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201301058
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Investigation of the intermolecular acyl‐transfer reactivity in molecular crystals of <italic>myo</italic>‐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 (CO) and 2) the molecular assembly, reinforced by CH⋅⋅⋅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‐<italic>p</italic>‐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 <italic>p</italic>‐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.</p> </abstract>