Elucidating Conformation and Hydrogen-Bonding Motifs of Reactive Thiourea Intermediates.

ABSTRACT: Substituted diphenylthioureas (DPTUs) are efficient hydrogen-bonding organo-catalysts, and substitution of DPTUs has been shown to greatly affect catalytic activity. Yet, both the conformation of DPTUs in solution and the conformation and hydrogen-bonded motifs within catalytically active intermediates, pertinent to their mode of activation, have remained elusive. By combining linear and ultrafast vibrational spectroscopy with spectroscopic simulations and calculations, we show that different conformational states of thioureas give rise to distinctively different N-H stretching bands in the infrared spectra. In the absence of hydrogen-bond-accepting substrates, we show that vibrational structure and dynamics are highly sensitive to the substitution of DPTUs with CF₃ groups and t

SUBMITTER: Ehrhard AA 

PROVIDER: S-EPMC9594049 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature