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A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible β-Hydrogens

DFT calculations have been performed on the palladium-catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C-N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non-polar solvents, th... Full description

Journal Title: Chemistry (Weinheim an der Bergstrasse Germany), 01 March 2016, Vol.22(10), pp.3422-3429
Main Author: Hao, Wei
Other Authors: Wei, Junnian , Chi, Yue , Walsh, Patrick J , Xi, Zhenfeng
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1521-3765 ; PMID: 26807680 Version:1 ; DOI: 10.1002/chem.201503910
Link: http://pubmed.gov/26807680
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title: A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible β-Hydrogens
format: Article
creator:
  • Hao, Wei
  • Wei, Junnian
  • Chi, Yue
  • Walsh, Patrick J
  • Xi, Zhenfeng
subjects:
  • Alkylpalladium Iodide Complexes
  • Computational Chemistry
  • Reaction Mechanisms
  • Reductive Elimination
  • Synthetic Methods
ispartof: Chemistry (Weinheim an der Bergstrasse, Germany), 01 March 2016, Vol.22(10), pp.3422-3429
description: DFT calculations have been performed on the palladium-catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C-N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non-polar solvents, thus promoting reductive elimination and preventing β-hydride elimination. The C-N bond cleavage process was explored and the computations show that PPh is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiOtBu is not necessary for the oxidative addition, alkyne insertion, or C-N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover-limiting steps were found to be C-N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction.
language: eng
source:
identifier: E-ISSN: 1521-3765 ; PMID: 26807680 Version:1 ; DOI: 10.1002/chem.201503910
fulltext: fulltext
issn:
  • 15213765
  • 1521-3765
url: Link


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titleA DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible β-Hydrogens
creatorHao, Wei ; Wei, Junnian ; Chi, Yue ; Walsh, Patrick J ; Xi, Zhenfeng
ispartofChemistry (Weinheim an der Bergstrasse, Germany), 01 March 2016, Vol.22(10), pp.3422-3429
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subjectAlkylpalladium Iodide Complexes ; Computational Chemistry ; Reaction Mechanisms ; Reductive Elimination ; Synthetic Methods
descriptionDFT calculations have been performed on the palladium-catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C-N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non-polar solvents, thus promoting reductive elimination and preventing β-hydride elimination. The C-N bond cleavage process was explored and the computations show that PPh is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiOtBu is not necessary for the oxidative addition, alkyne insertion, or C-N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover-limiting steps were found to be C-N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction.
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descriptionDFT calculations have been performed on the palladium-catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C-N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non-polar solvents, thus promoting reductive elimination and preventing β-hydride elimination. The C-N bond cleavage process was explored and the computations show that PPh is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiOtBu is not necessary for the oxidative addition, alkyne insertion, or C-N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover-limiting steps were found to be C-N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction.
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abstractDFT calculations have been performed on the palladium-catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C-N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non-polar solvents, thus promoting reductive elimination and preventing β-hydride elimination. The C-N bond cleavage process was explored and the computations show that PPh is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiOtBu is not necessary for the oxidative addition, alkyne insertion, or C-N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover-limiting steps were found to be C-N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction.
doi10.1002/chem.201503910
pmid26807680
date2016-03-01