N‐heterocyclic Carbene Palladium(II) Amine Complexes: The Role of Primary Aryl‐ or Alkylamines Binding and their Applications in Buchwald‐Hartwig Amination Reaction

2021 ◽  
Author(s):  
Ming-Tsz Chen ◽  
Yu-Cheng Hsu
Keyword(s):  
Amine Complexes ◽  
Amination Reaction

scholarly journals The Mechanism of Rhodium Catalyzed Allylic C–H Amination

2019 ◽  
Author(s):  
Robert Harris ◽  
Jiyong Park ◽  
Taylor Nelson ◽  
Nafees Iqbal ◽  
Daniel Salgueiro ◽  
...  
Keyword(s):  
Acid Catalyst ◽  
Reductive Elimination ◽  
Quantum Mechanical ◽  
Allylic Amination ◽  
Reaction Conditions ◽  
Allyl Complex ◽  
Acetate Ligand ◽  
Amination Reaction ◽  
Lewis Acid Catalyst

The mechanism of catalytic allylic C–H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate that allylic C–H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidant in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetry<b></b>experiments support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand. Lastly, evidences supporting the amination of an allylic acetate intermediate is presented. Both nucleophilic substitution catalyzed by Ag<sup>+</sup>that behaves as a Lewis acid catalyst and an inner-sphere amination catalyzed by Cp*Rh are shown to be viable for the last step of the allylic amination reaction.

The collaborative role of molecular conformation and energetics in the binding of gas-phase non-covalent polymer/amine complexes

2012 ◽  
Vol 14 (1) ◽  
pp. 165-172 ◽  
Author(s):  
Justin B. Renaud ◽  
Eric Martineau ◽  
Gleb G. Mironov ◽  
Maxim V. Berezovski ◽  
Paul M. Mayer
Keyword(s):  
Gas Phase ◽  
Molecular Conformation ◽  
Amine Complexes

scholarly journals Conformational insights and vibrational study of a promising anticancer agent: the role of the ligand in Pd(ii)–amine complexes

2015 ◽  
Vol 39 (8) ◽  
pp. 6274-6283 ◽  
Author(s):  
Sónia M. Fiuza ◽  
Ana M. Amado ◽  
Stewart F. Parker ◽  
Maria Paula M. Marques ◽  
Luís A. E. Batista de Carvalho
Keyword(s):  
Anticancer Agent ◽  
Vibrational Analysis ◽  
Amine Complexes ◽  
Vibrational Study

This study reports the first complete vibrational analysis of a dinuclear polyamine-based compound displaying antitumour properties.

scholarly journals The Mechanism of Rhodium Catalyzed Allylic C–H Amination

2019 ◽  
Author(s):  
Robert Harris ◽  
Jiyong Park ◽  
Taylor Nelson ◽  
Nafees Iqbal ◽  
Daniel Salgueiro ◽  
...  
Keyword(s):  
Acid Catalyst ◽  
Reductive Elimination ◽  
Quantum Mechanical ◽  
Allylic Amination ◽  
Reaction Conditions ◽  
Allyl Complex ◽  
Acetate Ligand ◽  
Amination Reaction ◽  
Lewis Acid Catalyst

The mechanism of catalytic allylic C–H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate that allylic C–H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidant in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetry<b></b>experiments support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand. Lastly, evidences supporting the amination of an allylic acetate intermediate is presented. Both nucleophilic substitution catalyzed by Ag<sup>+</sup>that behaves as a Lewis acid catalyst and an inner-sphere amination catalyzed by Cp*Rh are shown to be viable for the last step of the allylic amination reaction.

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