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Exploring the Conversion of Macrocyclic 2,2'-Biaryl Bis(thioureas) into Cyclic Monothioureas: An Experimental and
Mateo Alajarin1, Carmen Lopez-Leonardo1, Raul-Angel Orenes2
1Department of Organic Chemistry, Faculty of Chemistry , University of Murcia , Regional Campus of International Excellence "Campus Mare Nostrum", 30100 Murcia , Spain.
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.
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