Cyanide Anion as a Leaving Group in Nucleophilic Aromatic Substitution: Synthesis of Quaternary Centers at Azine Heterocycles

2012 ◽  
Vol 78 (2) ◽  
pp. 762-769 ◽  
Author(s):  
Alexander D. Thompson ◽  
Malcolm P. Huestis
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Cyanide Anion ◽  
Quaternary Centers ◽  
Leaving Group

scholarly journals The Truce–Smiles rearrangement and related reactions: a review

2017 ◽  
Vol 95 (5) ◽  
pp. 483-504 ◽  
Author(s):  
Anna R.P. Henderson ◽  
Joel R. Kosowan ◽  
Tabitha E. Wood
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Future Research ◽  
Tandem Reaction ◽  
Aromatic Substitution ◽  
Smiles Rearrangement ◽  
Research Directions ◽  
Reaction Method ◽  
Design Variables ◽  
Leaving Group ◽  
Future Research Directions

The Truce–Smiles rearrangement is an X → C aryl migration reaction that is achieved by an intramolecular nucleophilic aromatic substitution pathway. The reaction exhibits a wide substrate scope with respect to a migrating aryl ring and leaving group, appearing in many different tandem reaction sequences, to achieve a wide variety of product outcomes. We present an extensive survey of reported examples of the Truce–Smiles rearrangement from the chemistry literature (1950s until present) organized by various substrate design variables or aspects of the reaction method. Present deficiencies in our understanding of the reaction are identified with recommendations for future research directions and useful developments in the application of the reaction are celebrated.

A new leaving group in nucleophilic aromatic substitution reactions (SNAr)

2008 ◽  
Vol 2008 (8) ◽  
pp. 432-433 ◽  
Author(s):  
Mehdi Bakavoli ◽  
Mehdi Pordel ◽  
Mohammad Rahimizadeh ◽  
Pooneh Jahandari
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Leaving Group

Mechanisms and models for homogeneous copper mediated ligand exchange reactions of the type: CuNu + ArX → ArNu + CuX

1985 ◽  
Vol 63 (1) ◽  
pp. 111-120 ◽  
Author(s):  
Christiane Couture ◽  
Anthony James Paine
Keyword(s):  
Molecular Design ◽  
Nucleophilic Aromatic Substitution ◽  
Common Mechanism ◽  
Aromatic Substitution ◽  
Exchange Reactions ◽  
Design And Synthesis ◽  
Alkyl Groups ◽  
Leaving Group ◽  
First Time ◽  
Redox Equilibria

The title reactions are an important class of copper mediated nucleophilic aromatic substitution processes, which constitute a useful tool in the molecular design and synthesis of small molecules. We report the results of extensive investigation of these processes, primarily focussing on cyanodeiodination (ArI + CuCN → CuI + ArCN). Among the interesting features of these processes are: (a) an unusual rate equation involving autocatalysis by CuI product; (b) retardation by both excess nucleophile (as KCN) and excess leaving group (as KI), which compete with ArX to complex with CuNu; (c) only cuprous nucleophiles are active (ligand exchanged products from cupric salts arise from prior redox equilibria which form CuNu); (d) the halogen effect is large (kI ~ 40–100 kBr ~ 300–5000kCl) but the Hammett ρ value is zero; (e) ortho-alkyl groups do not hinder the reaction (and actually cause mild acceleration by relief of steric strain). Finally, the introduction of an ortho-COO− group accelerates the reaction by a factor of 104–105, but the general features of the accelerated reactions are also the same, again indicating a common mechanism, with entropic acceleration by ortho-carboxylate. Both kinetic and thermodynamic factors were considered in detail, the latter apparently for the first time. Applications to practical syntheses are considered, and novel mechanistic models for these interesting processes are discussed.

Methylsulfone as a leaving group for synthesis of hyperbranched poly(arylene pyrimidine ether)s by nucleophilic aromatic substitution

RSC Advances ◽  
2015 ◽  
Vol 5 (17) ◽  
pp. 12821-12823 ◽  
Author(s):  
Yue Guan ◽  
Chunbo Wang ◽  
Daming Wang ◽  
Guodong Dang ◽  
Chunhai Chen ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Hyperbranched Poly ◽  
Leaving Group

Using a novel leaving group, methylsulfone activated by pyrimidine, 4,6-dichloro-2-(methylsulfonyl)pyrimidine was used to synthesize two new hyperbranched poly(arylene pyrimidine ether)s with diphenol via a nucleophilic substitution polymerization.

Sign in / Sign up

Export Citation Format

Share Document