Publication: Exploring the Conversion of Macrocyclic 2,2 '-Biaryl Bis(thioureas) into Cyclic Monothioureas: An Experimental and Computational Investigation
Authors
Alajarín, Mateo ; Lopez-Leonardo, Carmen ; Orenes, Raul A. ; Pastor Vivero, Aurelia ; Sanchez-Andrada, Pilar ; Vidal, Angel
item.page.secondaryauthor
item.page.director
Publisher
American Chemical Society
publication.page.editor
publication.page.department
DOI
10.1021/acs.joc.8b02496
item.page.type
info:eu-repo/semantics/article
Description
Abstract
Macrocyclic bis(thioureas) derived from 2,2’-biphenyl and binaphthyl skeletons have been synthesized by reaction of 2,2’-diaminobiaryl and 2,2’-bis(isothiocyanato)biaryl derivatives. The splitting of these bis(thioureas) into two units of the respective cyclic monothioureas has been monitored by NMR, shedding some light on the factors that control these processes. Additionally, a computational study revealed up to three mechanistic paths for the conversion of the 2,2’-biphenyl-derived bis(thiourea) into the corresponding monothiourea. The proposed mechanisms account for the participation of a molecule of water as an efficient proton-switch, as well as for different classes of putative intermediates. The computational study also supports the ability of the thiourea group to participate in a plethora of processes, such as prototropic equilibria, sigmatropic shifts, heteroene and retro-heteroene reactions, and cis-trans isomerizations.
publication.page.subject
Citation
J. Org. Chem. 2018, 83, 14022–14035.
item.page.embargo
Collections
Ir a Estadísticas
Este ítem está sujeto a una licencia Creative Commons. http://creativecommons.org/licenses/by-nc-nd/3.0/es/