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Clean and selective catalytic C-H alkylation of alkenes with environmental friendly alcohols

Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science 2011, 333, 1613] allow the formation of a CC bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the CO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic CH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments

We thank King Abdullah University of Science and Technology (CFF project) for support. A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN

Elsevier

Manager: Ministerio de Econom铆a y Competitividad (Espanya)
Author: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Polo Ortiz, Alfonso
Cavallo, Luigi
Abstract: Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science 2011, 333, 1613] allow the formation of a CC bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the CO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic CH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments
We thank King Abdullah University of Science and Technology (CFF project) for support. A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN
Document access: http://hdl.handle.net/2072/299800
Language: eng
Publisher: Elsevier
Rights: Tots els drets reservats
Subject: Alquilaci贸
Alkylation
Funcional de densitat, Teoria del
Density functionals
Catalitzadors de rodi
Rhodium catalyst
Title: Clean and selective catalytic C-H alkylation of alkenes with environmental friendly alcohols
Type: info:eu-repo/semantics/article
Repository: Recercat

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