Synthesis of Sultones from Chlorosulfates by a Complex Cascade Reaction Occurring under Mild Thermal Conditions |
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Authors: | Dr Lara Cala Dr Iván Rivilla Prof Dr Fernando P Cossío Prof Dr Francisco J Fañanás Prof Dr Félix Rodríguez |
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Institution: | 1. Instituto Universitario de Química Organometálica “Enrique Moles”, Universidad de Oviedo, Julián Clavería, 8, 33006 Oviedo, Spain;2. Departamento de Química Orgánica I, Universidad del, País Vasco (UPV/EHU) and Donostia International Physics Center (DIPC), P. K. 1072, 20080 San Sebastián, Spain |
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Abstract: | Chlorosulfate derivatives are interesting reagents that have been traditionally used to get other sulfur-containing compounds by formal nucleophilic substitution of the chlorine atom. This work describes a different mode of reactivity of alkyne-containing chlorosulfates to get sultones, the sulfur analogues of lactones. The complex skeletal rearrangement observed in this transformation is comparable to those intricate processes promoted or catalyzed by organometallic compounds. However, the reaction here described does not require any reagent or additive, being just a thermal process. Computational calculations support a mechanism based on a series of cascade reactions where almost every step is counterintuitive. Some of these steps include original processes related to classical reactions, thus adding complementary views to traditional organic chemistry. |
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Keywords: | density functional calculations domino reactions pericyclic reactions ring expansion sulfur heterocycles |
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