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Torsional and Electronic Factors Control the C−H⋅⋅⋅O Interaction

DOI: 10.1002/chem.201602905 DOI Help

Authors: Russell W. Driver (Chemistry Research Laboratory, University of Oxford) , Timothy D. W. Claridge (Chemistry Research Laboratory, University of Oxford) , Steve Scheiner (Department of Chemistry and Biochemistry, Utah State University) , Martin D. Smith (Chemistry Research Laboratory, University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry - A European Journal , VOL 22 , PAGES 16513 - 16521

State: Published (Approved)
Published: November 2016
Diamond Proposal Number(s): 7768

Open Access Open Access

Abstract: The precise role of non-conventional hydrogen bonds such as the C−H⋅⋅⋅O interaction in influencing the conformation of small molecules remains unresolved. Here we survey a series of β-turn mimetics using X-ray crystallography and NMR spectroscopy in conjunction with quantum calculation, and conclude that favourable torsional and electronic effects are important for the population of states with conformationally influential C−H⋅⋅⋅O interactions. Our results also highlight the challenge in attempting to deconvolute a myriad of interdependent noncovalent interactions in order to focus on the contribution of a single one. Within a small molecule that is designed to resemble the complexity of the environment within peptides and proteins, the interplay of different steric burdens, hydrogen-acceptor/-donor properties and rotational profiles illustrate why unambiguous conclusions based solely on NMR chemical shift data are extremely challenging to rationalize.

Journal Keywords: crystallography; density functional calculations; foldamers; hydrogen bonds; NMR spectroscopy

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 21/11/2016 10:01


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