Chemically triggered C-ON bond homolysis in alkoxyamines. Part 7. Remote polar effect

2014 ◽  
Vol 27 (5) ◽  
pp. 387-391 ◽  
Author(s):  
Gérard Audran ◽  
Matisse Bim Batsiandzy Ibanou ◽  
Paul Brémond ◽  
Sylvain R. A. Marque ◽  
Germain Obame ◽  
...  
Keyword(s):  
Polar Effect ◽  
Bond Homolysis

scholarly journals How intramolecular hydrogen bonding (IHB) controls the C–ON bond homolysis in alkoxyamines

2017 ◽  
Vol 15 (39) ◽  
pp. 8425-8439 ◽  
Author(s):  
Gérard Audran ◽  
Raphael Bikanga ◽  
Paul Brémond ◽  
Mariya Edeleva ◽  
Jean-Patrick Joly ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Bond Homolysis ◽  
Intramolecular Hydrogen

IHB between alkyl and nitroxyl fragments affords striking changes in kd, affording a nice control of the C–ON bond homolysis.

pH-Sensitive C–ON Bond Homolysis of Alkoxyamines of Imidazoline Series: A Theoretical Study

2014 ◽  
Vol 118 (20) ◽  
pp. 5542-5550 ◽  
Author(s):  
Dmitriy A. Parkhomenko ◽  
Mariya V. Edeleva ◽  
Vitaly G. Kiselev ◽  
Elena G. Bagryanskaya
Keyword(s):  
Theoretical Study ◽  
Ph Sensitive ◽  
Bond Homolysis

Unique carbon–carbon bond homolysis in 3-alkylcyclohexa-1,4-dienyl-3-carboxylic acid radicals

1996 ◽  
pp. 2199-2200 ◽  
Author(s):  
Paul A. Baguley ◽  
Gavin Binmore ◽  
Aynsley Milne ◽  
John C. Walton
Keyword(s):  
Carboxylic Acid ◽  
Carbon Bond ◽  
Carbon Carbon Bond ◽  
Bond Homolysis

OO bond homolysis in hydrogen peroxide

2017 ◽  
Vol 38 (25) ◽  
pp. 2186-2192 ◽  
Author(s):  
Lakshmanan Sandhiya ◽  
Hendrik Zipse
Keyword(s):  
Hydrogen Peroxide ◽  
Bond Homolysis

THE TRANSMISSION OF POLAR EFFECTS: PART II. THE KINETICS OF ESTERIFICATION WITH DIAZODIPHENYLMETHANE AND THE IONIZATION OF 3-SUBSTITUTED ACRYLIC ACIDS

1965 ◽  
Vol 43 (12) ◽  
pp. 3354-3363 ◽  
Author(s):  
Keith Bowden
Keyword(s):  
Butyl Alcohol ◽  
Polar Effect ◽  
Rate Coefficients ◽  
Strengthening Effect ◽  
Benzoic Acids ◽  
Linear Free Energy ◽  
Substituted Benzoic Acids ◽  
Energy Relations ◽  
Acrylic Acids ◽  
Kinetics Of

The rate coefficients for the reaction with diazodiphenylmethane in ethanol, t-butyl alcohol, and ethyl acetate at 30° and the pKa values in water at 25° of fourteen 3-substituted acrylic acids have been determined. The effect of substitution is assessed by use of linear free energy relations. A definite incremental acid-strengthening effect solely due to cis-substitution is confirmed. This is not a "bulk" steric effect and is due solely to the orientation of substitution. The polar effect of a substituent is found to be approximately the same from the cis- or trans-position. An attempt is made to test the suggested mechanisms for the transmission of the polar effect. In the reactions studied the transmission of the polar effect in 3-substituted acrylic acid and ortho-substituted benzoic acids is approximately twice that of the meta- or para-substituted benzoic acids. This appears to be reasonably accommodated by a significant field effect.

Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Synthesis ◽  
2017 ◽  
Vol 49 (15) ◽  
pp. 3269-3280 ◽  
Author(s):  
Tobias Parchomyk ◽  
Konrad Koszinowski
Keyword(s):  
Catalyst Activity ◽  
Cross Coupling ◽  
Short Review ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Open Questions ◽  
Carbon Carbon Bonds ◽  
Bond Homolysis ◽  
Molecular Complexity ◽  
Synthetic Application

Iron-catalyzed cross-coupling reactions provide a promising way to form new carbon–carbon bonds and build up molecular complexity. This short review presents recent advances in the synthetic application of these reactions as well as in the elucidation of their mechanism. It also highlights remaining problems and aims at pointing out ways toward possible remedies.1 Introduction2 Synthesis: Recent Accomplishments and Unsolved Problems2.1 Substrate Scope: Electrophiles2.2 Substrate Scope: Nucleophiles2.3 Catalyst Activity and Chemoselectivity2.4 Stereoselectivity2.5 Practical Aspects3 Mechanism: Recent Insights and Open Questions3.1 Transmetallation and Activation of the Iron Precatalyst3.2 Coupling via Oxidative Addition and Reductive Elimination3.3 Coupling via C–X Bond Homolysis and Radical Rebound3.4 Coupling via Bimolecular C–X Bond Homolysis3.5 Other Reactions of Organoiron Species with Electrophiles4 Toward Rational Reaction Improvement5 Conclusion

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