Competitive Intramolecular Hydrogen Bonding: Offering Molecules a Choice

Author:

Sun Yu1,Morton Evelyn R.1,Bhabha Hunaida1,Clark Ewan R.2,Bučar Dejan‐Krešimir1ORCID,Barros‐Metlova Victoria1,Gould Jamie A.1ORCID,Aliev Abil E.1,Haynes Cally J. E.1ORCID

Affiliation:

1. Chemistry Department University College London 20 Gordon Street London WC1H 0AJ UK

2. School of Chemistry and Forensics University of Kent Canterbury CT2 7NH UK

Abstract

AbstractThe conformational preferences of N‐((6‐methylpyridin‐2‐yl)carbamothioyl)benzamide were studied in solution, the gas phase and the solid state via a combination of NMR, density functional theory (DFT) and single crystal X‐ray techniques. This acyl thiourea derivative can adopt two classes of low energy conformation, each stabilized by a different 6‐membered intramolecular hydrogen bond (IHB) pseudoring. Analysis in different solvents revealed that the conformational preference of this molecule is polarity dependent, with increasingly polar environments yielding a higher proportion of the minor conformer containing an NH⋅⋅⋅N IHB. The calculated barrier to interconversion is consistent with dynamic behaviour at room temperature, despite the propensity of 6‐membered IHB pseudorings to be static. This work demonstrates that introducing competitive IHB pathways can render static IHBs more dynamic and that such systems could have potential as chameleons in drug design.

Funder

University College London

Publisher

Wiley

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