Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes

Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes

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.

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Bibliographic Details
Main Authors: Cruz, Daniel A., Sinka, Victoria, de Armas, Pedro, Steingruber, Hugo Sebastián, Fernández, Israel, Martín, Víctor S., Miranda, Pedro O., Padrón, Juan I.
Other Authors: Ministerio de Ciencia, Innovación y Universidades (España)
Format: artículo biblioteca
Language:English
Published: American Chemical Society 2021-08-06
Subjects:Hydrocarbons, Addition reactions, Oxygen, Chemical reactions, Selectivity,
Online Access:http://hdl.handle.net/10261/246803
http://dx.doi.org/10.13039/501100011033
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spelling dig-ipna-es-10261-2468032021-08-06T13:26:44Z Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes Cruz, Daniel A. Sinka, Victoria de Armas, Pedro Steingruber, Hugo Sebastián Fernández, Israel Martín, Víctor S. Miranda, Pedro O. Padrón, Juan I. Ministerio de Ciencia, Innovación y Universidades (España) Agencia Estatal de Investigación (España) Gobierno de Canarias Cabildo de Tenerife Universidad de Santiago de Compostela Hydrocarbons Addition reactions Oxygen Chemical reactions Selectivity 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. Peer reviewed 2021-07-29T08:27:46Z 2021-07-29T08:27:46Z 2021-08-06 artículo http://purl.org/coar/resource_type/c_6501 Organic Letters 23(15): 6105–6109 (2021) 1523-7060 http://hdl.handle.net/10261/246803 10.1021/acs.orglett.1c02186 1523-7052 http://dx.doi.org/10.13039/501100011033 en #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# MICIU/PGC2018- 094503-B-C22 MICINN/PID2019-106184GB/I00 Publisher's version https://doi.org/10.1021/acs.orglett.1c02186 Sí open American Chemical Society
institution IPNA ES
collection DSpace
country España
countrycode ES
component Bibliográfico
access En linea
databasecode dig-ipna-es
tag biblioteca
region Europa del Sur
libraryname Biblioteca del IPNA España
language English
topic Hydrocarbons
Addition reactions
Oxygen
Chemical reactions
Selectivity
Hydrocarbons
Addition reactions
Oxygen
Chemical reactions
Selectivity
spellingShingle Hydrocarbons
Addition reactions
Oxygen
Chemical reactions
Selectivity
Hydrocarbons
Addition reactions
Oxygen
Chemical reactions
Selectivity
Cruz, Daniel A.
Sinka, Victoria
de Armas, Pedro
Steingruber, Hugo Sebastián
Fernández, Israel
Martín, Víctor S.
Miranda, Pedro O.
Padrón, Juan I.
Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
description 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.
author2 Ministerio de Ciencia, Innovación y Universidades (España)
author_facet Ministerio de Ciencia, Innovación y Universidades (España)
Cruz, Daniel A.
Sinka, Victoria
de Armas, Pedro
Steingruber, Hugo Sebastián
Fernández, Israel
Martín, Víctor S.
Miranda, Pedro O.
Padrón, Juan I.
format artículo
topic_facet Hydrocarbons
Addition reactions
Oxygen
Chemical reactions
Selectivity
author Cruz, Daniel A.
Sinka, Victoria
de Armas, Pedro
Steingruber, Hugo Sebastián
Fernández, Israel
Martín, Víctor S.
Miranda, Pedro O.
Padrón, Juan I.
author_sort Cruz, Daniel A.
title Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
title_short Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
title_full Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
title_fullStr Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
title_full_unstemmed Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
title_sort iron(ii) and copper(i) control the total regioselectivity in the hydrobromination of alkenes
publisher American Chemical Society
publishDate 2021-08-06
url http://hdl.handle.net/10261/246803
http://dx.doi.org/10.13039/501100011033
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