Nucleophilic Displacement in the Benzene Series<sup>1</sup>

Berliner, Ernst; Monack, Louise

doi:10.1021/ja01126a069

Cited by 56 publications

(44 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…While it has been found possible to set up a fixed scale of inductive effects covering all reaction types, analysis of the resonance contributions by R = URPI (26) gave widely scattered values of UR in accord with the findings of Bekkum, Verkade and Wepster. For msubstituents generally and for p-substituents in "insulated" reaction series, where the reaction center is separated from the ring by one or more methylene groups, an unenhanced aRO-value is obtainable from which are derived…”

Section: M-coz-supporting

confidence: 71%

Linear Free Energy Relationships.

Wells¹

1963

Chem. Rev.

531

313

View full text Add to dashboard Cite

Section: M-coz-supporting

confidence: 71%

Linear Free Energy Relationships.

Wells¹

1963

Chem. Rev.

531

313

View full text Add to dashboard Cite

“…It is important to realize that E S ( r ) cannot always be used as a black‐box approach when analyzing S N Ar reactions, but that the interpretation of the computational results requires chemical knowledge to enable prediction of positional selectivity and reactivity. This can be exemplified by our analysis of a dataset by Berliner and Monack, on S N Ar reactions in a series of 1‐bromo‐4‐ R ‐2‐nitrobenzene compounds . The original experimental study was performed in piperidine and piperidine also functioned as the nucleophile .…”

Section: Molecular Surface Propertiesmentioning

confidence: 99%

“…This can be exemplified by our analysis of a dataset by Berliner and Monack, on S N Ar reactions in a series of 1‐bromo‐4‐ R ‐2‐nitrobenzene compounds . The original experimental study was performed in piperidine and piperidine also functioned as the nucleophile . It is exclusively the bromide that is substituted under the experimental conditions.…”

Section: Molecular Surface Propertiesmentioning

confidence: 99%

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Brinck

Stenlid

2018

Advcd Theory and Sims

View full text Add to dashboard Cite

The current status of the molecular surface property approach (MSPA) and its application for analysis and prediction of intermolecular interactions, including chemical reactivity, are reviewed. The MSPA allows for identification and characterization of all potential interaction sites of a molecule or nanoparticle by the computation of one or more molecular properties on an electronic isodensity surface. A wide range of interactions can be analyzed by three properties, which are well-defined within Kohn-Sham density functional theory. These are the electrostatic potential, the average local ionization energy, and the local electron attachment energy. The latter two do not only reflect the electrostatic contribution to a chemical interaction, but also the contributions from polarization and charge transfer. It is demonstrated that the MSPA has a high predictive capacity for non-covalent interactions, for example, hydrogen and halogen bonding, as well as organic substitution and addition reactions. The latter results open up applications within drug design and medicinal chemistry. The application of MSPA has recently been extended to nanoparticles and extended surfaces of metals and metal oxides. In particular, nanostructural effects on the catalytic properties of noble metals are rationalized. The potential for using MSPA in rational design of heterogeneous catalysts is discussed. Tore Brinck is professor of physical chemistry at KTH Royal Institute of Technology in Stockholm, Sweden. He received his M.Sc. in chemical engineering from KTH in 1990, and his Ph.D. from the University of New Orleans in 1993 with Prof. Peter Politzer as Ph.D. advisor. His research involves the development of electronic descriptors for the analysis of chemical reactivity, as well as the application of electronic structure methods to the analysis of chemical reactions in condensed phases. He also uses computational chemistry to study enzyme design, heterogeneous catalysis, and energetic materials. Joakim Halldin Stenlid is a postdoctoral fellow in the group of Prof. Lars GM Pettersson at Stockholm University where he is carrying out computational studies in electrochemistry and heterogeneous catalysis. He obtained his Ph.D. in physical chemistry from KTH

show abstract

“…49,55,56 Nucleophilic aromatic substitution rates are strongly influenced by the electrophilicity of the aryl halide. Mild nucleophilic aromatic substitutions require polar solvents and aromatic systems containing nitro activating groups.…”

Section: Scheme 15mentioning

confidence: 99%

Carbon−Heteroatom Bond-Forming Reductive Eliminations of Amines, Ethers, and Sulfides

1998

View full text Add to dashboard Cite

Elementary transition metal-mediated reactions that form and cleave the bonds of organic molecules are the foundation of homogeneous catalysis. Such bond cleavage and formation often occurs by oxidative addition and reductive elimination. As shown in Scheme 1, these two reactions are essentially the same process in opposite directions: oxidative addition increases the oxidation state of the metal by two, decreases the d-electron count by two, and increases the overall number of valence electrons by two, while reductive elimination inflicts the opposite two-electron changes. Thermodynamic factors dictate whether a complex will undergo elimination or addition.The formation of carbon-hydrogen and carboncarbon bonds by reductive elimination is now common. Catalytic hydrogenation of alkenes, hydroformylation, alkene arylation (Heck reaction), and cross-coupling processes all involve C-H and C-C bond-forming reductive eliminations. The formation of carbon-heteroatom bonds by reductive elimination is less common, and just five years ago reductive elimination reactions that form C-O, C-N, and C-S bonds in ethers, amines, and sulfides had not been observed directly. It was unclear whether a kinetic barrier prevented these classes of reductive elimination, whether these eliminations were disfavored thermodynamically, or whether appropriate compounds to observe these reactions simply had not been prepared.During the past five years, palladium-catalyzed chemistry that produces arylamines from aryl halides and either primary or secondary amines has been developed, 1-4 and a catalytic cycle that is supported by detailed mechanistic studies 5 is provided in Scheme 2. It seemed likely that the amination process, first reported with tin amides by Kosugi and Migita over 10 years ago, 6,7 involved reductive elimination of amine. It, therefore, seemed to the members of my research group that the generation of stable palladium amido aryl complexes would allow for the direct observation of C-N bond-forming reductive elimination of amines.In addition, similar palladium-and nickel-catalyzed reactions that form aryl sulfides have been reported, [8][9][10][11][12][13][14] and again, generation of stable thiolato aryl complexes would allow for the direct observation of C-S bondforming reductive elimination of sulfides. Information on how these reactions occur might lead to improvements upon the catalytic formation of amines and sulfides. Finally, these studies may reveal systems that would undergo reductive elimination chemistry to form the C-O bonds in aryl ethers. As a result of this work, palladiumand nickel-catalyzed amination of aryl halides has become a general process 1-4 and new chemistry that forms aryl ethers has been developed recently. [15][16][17][18][19] Reviews of the catalytic carbon-heteroatom bond-forming coupling processes have been published recently. [20][21][22] This Account describes work in my laboratory, along with related work from other groups, on the discovery of complexes that reductively eliminate amines, ethe...

show abstract

Nucleophilic Displacement in the Benzene Series¹

Cited by 56 publications

References 3 publications

Linear Free Energy Relationships.

Linear Free Energy Relationships.

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Carbon−Heteroatom Bond-Forming Reductive Eliminations of Amines, Ethers, and Sulfides

Contact Info

Product

Resources

About

Nucleophilic Displacement in the Benzene Series1

Cited by 56 publications

References 3 publications

Linear Free Energy Relationships.

Linear Free Energy Relationships.

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Carbon−Heteroatom Bond-Forming Reductive Eliminations of Amines, Ethers, and Sulfides

Contact Info

Product

Resources

About

Nucleophilic Displacement in the Benzene Series¹