Regioselective Aromatic Nucleophilic Substitution in N-Aryl-2-nitrosoanilines with Oxygen and Nitrogen Nucleophiles

Modern Nucleophilic Aromatic Substitution

Addition-substitution reactions of 2-thio-3-chloroacrylamides with carbon, nitrogen, oxygen, sulfur and selenium nucleophiles.

Synthetically versatile conjugate addition of a range of carbon, nitrogen, oxygen, sulfur and selenium nucleophiles to the highly functionalised 2-thio-3-chloroacrylamides is described. The stereochemical and synthetic features of this transformation are discussed in detail. In most instances, the nucleophile replaces the chloro substituent with retention of stereochemistry. With the oxygen nuc...

Nucleophilic aromatic substitution on aryl-amido ligands promoted by oxidizing osmium(IV) centers.

Addition of amine nucleophiles to acetonitrile solutions of the OsIV anilido complex TpOs(NHPh)Cl2 (1) [Tp = hydrotris(1-pyrazolyl)borate] gives products with derivatized anilido ligands, i.e., TpOs[NH-p-C6H4(N(CH2)5)]Cl2 (2) from piperidine and TpOs[NH-p-C6H4N(CH2)4]Cl2 (3) from pyrrolidine. These materials are formed in approximately 30% yield under anaerobic conditions, together with approxi...

A Greener and Efficient Method for Nucleophilic Aromatic Substitution of Nitrogen-Containing Fused Heterocycles.

A simple and efficient methodology for the nucleophilic aromatic substitution of nitrogen-containing fused heterocycles with interesting biological activities has been developed in an environmentally sound manner using polyethylene glycol (PEG-400) as the solvent, leading to the expected compounds in excellent yields in only five minutes.

Nucleophilic Substitution Reactions of Aryl Thiophene-2-carbodithioates with Pyridines in Acetonitrile

The kinetics of reactions between Z-aryl thiophene-2-carbodithioates and X-pyridines in acetonitrile at 60.0 C have been investigated. The Brönsted plots obtained for the pyridinolysis of aryl thiophene-2-carbodithioates are curved, with the center of curvature at pKa ~ 5.2 (pKa). The Brönsted plots for these nucleophilic reactions show a change in slope from a large (βX ≅ 0.78-0.87) to a small...