Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
| Autor: | Victoria Sinka, Daniel A. Cruz, Pedro de Armas, Israel Fernández, Pedro O. Miranda, Hugo Sebastián Steingruber, Juan I. Padrón, Víctor S. Martín |
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| Přispěvatelé: | Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Gobierno de Canarias, Cabildo de Tenerife, Universidad de Santiago de Compostela |
| Rok vydání: | 2021 |
| Předmět: |
Addition reaction
Letter Chemistry Organic Chemistry Markovnikov's rule chemistry.chemical_element Regioselectivity Biochemistry Chemical reaction Medicinal chemistry Copper Hydrocarbons Addition reactions Oxygen chemistry.chemical_compound Bromide Reagent Chemical reactions Selectivity Physical and Theoretical Chemistry |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname Digital.CSIC: Repositorio Institucional del CSIC Consejo Superior de Investigaciones Científicas (CSIC) Organic Letters |
| Popis: | A new method that allows the complete control of the regioselectivity of the hydrobromination reaction of alkenes is described. Herein, we report a radical procedure with TMSBr and oxygen as common reagents, where the formation of the anti-Markovnikov product occurs in the presence of parts per million amounts of the Cu(I) species and the formation of the Markovnikov product occurs in the presence of 30 mol % iron(II) bromide. Density functional theory calculations combined with Fukui’s radical susceptibilities support the obtained results. This research was supported by the Ministerio de Ciencia, Innovación y Universidades (MCIU), la Agencia Estatal de Investigación (AEI), Fondo Europeo de Desarrollo Regional (FEDER), and ACIISI (Gobierno de Canarias) (PGC2018-094503-B-C22, ProID2017010118, and PID2019-106184GB-I00). V.S. thanks the Spanish MCIU for an F.P.U. fellowship. D.A.C. and P.O.M. thank Cabildo de Tenerife for a postdoctoral Agustín de Bethancourt transfer contract and a Tenerife 2030 Programme (TF INNOVA 2016-2021”) contract alongside Marco Estratégico de Desarrollo Insular (MEDI) and Fondo de Desarrollo de Canarias (FDCAN), respectively. Thanks to F.L. and R.R. (CIQUS-USC) for the help with the EPR spectroscopy. |
| Databáze: | OpenAIRE |
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