Year: 2016
Type: article
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.
Source: Chemistry - A European Journal
Institutions: University of Oxford, Utah State University
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $2,368
Awards: G120984652, Emulating Nature through Asymmetric Catalysis, G2590737227, International Collaboration in Chemistry: CH--O H-bonds as Structural Elements for Synthesis and Catalysis, G4104599821, CH--O Hydrogen-Bonds as Structural Elements for Synthesis and Catalysis, G5357357400, G5540395714, G5878972985, G6493112188, G8470759830
OpenAlex ID: W2529379296