18651-57-5Relevant academic research and scientific papers
Iron(III)-catalyzed halogenations by substitution of sulfonate esters
Ortega, Nuria,Feher-Voelger, Andres,Brovetto, Margarita,Padron, Juan I.,Martin, Victor S.,Martin, Tomas
experimental part, p. 963 - 972 (2011/06/20)
A novel halogenation reaction from sulfonates catalyzed by iron(III) is described. The reaction can be performed as a stoichiometric or a catalytic version. This reaction provides a convenient strategy for the efficient access to structurally diverse secondary chlorides, bromides and iodides. The stereochemical course of the reaction is governed by the substrate and the experimental conditions. Secondary alcohols modified as quisylates or pysylates are substantially more reactive. Aliphatic quisylates proceed with overall inversion of configuration under catalytic conditions. Chemoselectivity in bismesylates was observed in favour of the secondary mesylate. Additionally, based on the experimental results, a possible catalytic cycle for the halogenation has been proposed.
Clarification of the stereochemical course of nucleophilic substitution of arylsulfonate-based nucleophile assisting leaving groups
Braddock, D. Christopher,Pouwer, Rebecca H.,Burton, Jonathan W.,Broadwith, Phillip
experimental part, p. 6042 - 6049 (2009/12/24)
(Chemical Equation Presented) Secondary alcohols modified as tosylates, PEG-sulfonates, or quisylates undergo inversion of configuration at the reacting center when treated with lithium halide in acetone at reflux, where the PEG-sulfonates and quisylates are substantially more reactive. In sterically hindered cases, elimination is a competing process. In contrast, when treated with TiCl4, simple secondary sulfonates give chloride products with partial inversion of configuration. Any observed retention of configuration in a given alkyl sulfonate substrate under these conditions is likely due to neighboring group participation or diastereoselective attack on a carbocation (or ion pair) rather than an SNi mechanism.
Catalytic decomposition of alkyl chloroformates by hexabutylguanidinium chloride
Foulon, Frederique,Fixari, Bernard,Picq, Dominique,Le Perchec, Pierre
, p. 3387 - 3390 (2007/10/03)
Hexabutylguanidinium chloride (0.5 molar %) efficiently decomposes alkyl chloroformates into chlorides, with low alkenes formation, via a S(N)2 mechanism as demonstrated from substituents effects and asymmetric chloride synthesis.
