ABSTRACT
The electrophilicity of 4 different 3-nitroindole derivatives has been evaluated by Mayr's linear free energy relationship (log k(20 °C) = sN(E + N)) and reveals unexpected values for aromatic compounds, in the nitrostyrene range. 3-Nitroindoles are sufficiently electrophilic to interact with a common diene namely the Danishefsky's diene at room temperature, in the absence of any activator, to furnish smoothly the dearomatized (4+2) cycloadducts in good yields.
ABSTRACT
The dearomatization of conventional nitroarenes by lithiated enolates derived from methyl vinyl ketones easily takes place, following a formal (4+2) cycloaddition process. While nitroindoles react readily with in situ generated conjugated enolates, the deaggregation of these latter species using HMPA extends the reaction scope to the more aromatic nitronaphthalenes and pyridines.
ABSTRACT
Poorly nucleophilic aromatic amines (nitroanilines, chloroanilines, etc.) react readily and selectively with trans-4-methoxy-3-buten-2-one, a convenient, effective and inexpensive surrogate for 3-butyn-2-one, to afford (Z)-enaminones. The efficiency of the reaction mostly lies in the use of water as a solvent, which enhances the reaction rate by a 45 to 200-fold factor with regard to other media.
ABSTRACT
Nucleophilic enamines add spontaneously on heteroarenes 3-nitroindole and benzofuran to form a new C-C bond. With nitroindole and enamine , an unprecedented dearomatizing formal ene reaction occurs in a totally regio- and diastereo-selective manner. With 3-nitrobenzofuran and enamine , the reaction course is different and leads to the generation of a dienylphenol.
ABSTRACT
A wide range of 2-aroylbenzothiazoles 3 including some pharmacologically relevant derivatives can be obtained in high yields by simply heating o-halonitrobenzenes 1, acetophenones 2, elemental sulfur, and N-methylmorpholine. This three-component nitro methyl coupling was found to occur in an excellent atom-, step-, and redox-efficient manner in which elemental sulfur played the role of nucleophile building block and redox moderating agent to fulfill electronic requirements of the global reaction.