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

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.

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch

References and Relationships

• Bibliographic citation: Torsional and Electronic Factors Control the C−H⋅⋅⋅O Interaction ; volume:22 ; number:46 ; year:2016 ; pages:16513-16521 ; extent:9 ; Chemistry - a European journal ; 22, Heft 46 (2016), 16513-16521 (gesamt 9)

Contributors, Places and Time

• Creator: Driver, Russell W. ; Claridge, Timothy D. W. ; Scheiner, Steve ; Smith, Martin D.

Further information

• DOI: 10.1002/chem.201602905
• URN: urn:nbn:de:101:1-2022103107180823138591
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 15.08.2025, 7:49 AM CEST