N–H⋯X interactions stabilize intra-residue C5 hydrogen bonded conformations in heterocyclic α-amino acid derivatives. Issue 44 (29th October 2021)

• Record Type: Journal Article
• Authors: Mundlapati, Venkateswara Rao; Imani, Zeynab; D'mello, Viola C.; Brenner, Valérie; Gloaguen, Eric; Baltaze, Jean-Pierre; Robin, Sylvie; Mons, Michel; Aitken, David J.
• Is Part Of: Chemical science. Volume 12:Issue 44(2021)
• Page Start: 14826
• Page End: 14832
• Publication Date: 2021-10-29
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1sc05014a
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : In 4-membered ring heterocyclic α-amino acid derivatives, extended conformations based on intraresidue C5 H-bonds can be stabilized by N–H⋯X H-bonds, making the combined C5–C6γ structures prominent in both gas phase and in weakly polar solutions. Abstract : Nature makes extensive and elaborate use of hydrogen bonding to assemble and stabilize biomolecular structures. The shapes of peptides and proteins rely significantly on N–H⋯OC interactions, which are the linchpins of turns, sheets and helices. The C5 H-bond, in which a single residue provides both donor and acceptor, is generally considered too weak to force the backbone to adopt extended structures. Exploiting the synergy between gas phase (experimental and quantum chemistry) and solution spectroscopies to decipher IR spectroscopic data, this work demonstrates that the extended C5-based conformation in 4-membered ring heterocyclic α-amino acid derivatives is significantly stabilized by the formation of an N–H⋯X H-bond. In this synergic system the strength of the C5 interaction remains constant while the N–H⋯X H-bond strength, and thereby the support provided by it, varies with the heteroatom.