Catalytic Enantioselective Synthesis of Atropisomeric Biaryls: A Cation-Directed Nucleophilic Aromatic Substitution Reaction

Modern Nucleophilic Aromatic Substitution

General Approach to the Synthesis of Prochiral Atropisomeric Biaryls

General approach to the synthesis of prochiral precursors of chiral atropisomeric biaryls based on several complementary methods has been developed. Biaryls were obtained in good to excellent yields depending on their structure and selected method of synthesis. Furthermore, we demonstrate a possibility of utilisation of the obtained compounds possessing 2 or 3 ortho substituents around the aryl...

Synthesis of polynitroxides based on nucleophilic aromatic substitution.

The scope and limitations of the synthesis of polynitroxides by nucleophilic substitution of electron-deficient fluorinated aromatic compounds are described. The method provides a facile route to the formation of polynitroxides exhibiting strong electron exchange between nitroxide groups.

Catalytic enantioselective synthesis of indanes by a cation-directed 5-endo-trig cyclization.

5-Endo-trig cyclizations are generally considered to be kinetically unfavourable, as described by Baldwin's rules. Consequently, observation of this mode of reaction under kinetic control is rare. This is usually ascribed to challenges in achieving appropriate approach trajectories for orbital overlap in the transition state. Here, we describe a highly enantio- and diastereoselective route to c...

A QM/MM study of a nucleophilic aromatic substitution reaction catalyzed by 4-chlorobenzoyl-CoA dehalogenase.

Calculated using a QM/MM method, the free energy profile for the conversion of 4-chlorobenzoate to 4-hydroxybenzoate catalyzed by 4-chlorobenzoyl-CoA dehalogenase indicates the existence of a stable Meisenheimer complex.