Mechanistic investigation of vinylic carbon–fluorine bond activation of perfluorinated cycloalkenes using Cp*2ZrH2 and Cp*2ZrHF

2010 ◽  
Vol 131 (11) ◽  
pp. 1122-1132 ◽  
Author(s):  
Bradley M. Kraft ◽  
Eric Clot ◽  
Odile Eisenstein ◽  
William W. Brennessel ◽  
William D. Jones
Keyword(s):  
Bond Activation ◽  
Mechanistic Investigation

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

scholarly journals A Detailed Kinetico-Mechanistic Investigation on the Palladium C–H Bond Activation in Azobenzenes and Their Monopalladated Derivatives

2020 ◽  
Vol 59 (23) ◽  
pp. 17123-17133
Author(s):  
Alen Bjelopetrović ◽  
Dajana Barišić ◽  
Zrinka Duvnjak ◽  
Ivan Džajić ◽  
Marina Juribašić Kulcsár ◽  
...  
Keyword(s):  
Bond Activation ◽  
Mechanistic Investigation

Mechanistic Investigation of Palladium-Catalyzed meta-C–H Bond Activation of Arenes with a Carboxyl Directing Group

2021 ◽  
Vol 86 (19) ◽  
pp. 13475-13480
Author(s):  
Huiling Li ◽  
Miao Yang ◽  
Liyuan Jin ◽  
Yun-Fang Yang ◽  
Yuan-Bin She
Keyword(s):  
Bond Activation ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Directing Group

scholarly journals Mechanistic Investigation of the Carbon–Iodine Bond Activation on the Niobium–Carbon Cluster

ACS Omega ◽  
2017 ◽  
Vol 2 (9) ◽  
pp. 5335-5347
Author(s):  
Turbasu Sengupta ◽  
Muntazir S. Khan ◽  
Sourav Pal
Keyword(s):  
Bond Activation ◽  
Carbon Cluster ◽  
Mechanistic Investigation

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

Cyclometalation of Aryl-Substituted Phosphinines through CH-Bond Activation: A Mechanistic Investigation

2013 ◽  
Vol 19 (39) ◽  
pp. 13087-13098 ◽  
Author(s):  
Leen E. E. Broeckx ◽  
Sabriye Güven ◽  
Frank J. L. Heutz ◽  
Martin Lutz ◽  
Dieter Vogt ◽  
...  
Keyword(s):  
Bond Activation ◽  
Mechanistic Investigation

Temperature-controlled redox-neutral ruthenium(ii)-catalyzed regioselective allylation of benzamides with allylic acetates

2016 ◽  
Vol 14 (32) ◽  
pp. 7691-7701 ◽  
Author(s):  
Rajendran Manikandan ◽  
Masilamani Jeganmohan
Keyword(s):  
Bond Activation ◽  
Regioselective Synthesis ◽  
Mechanistic Investigation ◽  
Temperature Controlled

Temperature controlled regioselective synthesis of ortho allyl and vinyl benzamides under redox-free conditions was reported. Detailed mechanistic investigation of the C–H bond activation and isomerization reactions was carried out.

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