Iron-Catalyzed Intermolecular Oxyamination of Terminal Alkenes Promoted by HFIP Using Hydroxylamine Derivatives

An atom-economical intermolecular iron-catalyzed oxyamination of alkenes is described herein. The insertion of oxygenated and nitrogenated moieties from the hydroxylamine substrate was observed with full regio- and chemo-selectivity for terminal alkenes in good yields. HFIP as a solvent appeared to have a synergistic effect with the iron catalyst to promote the formation of the oxyaminated products. Preliminary mechanistic studies suggest a pathway going through an aziridination reaction followed by an in situ ring opening

Reductive Cleavage of Aromatic and Heteroaromatic Ester Functions via Copper-Catalyzed Proto-Decarbomethoxylation

An unprecedented catalytic reductive cleavage of aromatic and heteroaromatic methyl ester functions was successfully achieved with a cheap, nontoxic, and air-stable Cu­(OAc)₂ catalyst. This reaction is fast, features good functional group tolerance, does not require inert atmosphere or anhydrous solvent, and can be scaled up to 1 g. Moreover, carboxylic acids and <i>t</i>-butyl esters also reacted smoothly under these conditions

Development of a One-Pot Four C–C Bond-Forming Sequence Based on Palladium/Ruthenium Tandem Catalysis

A one-pot four C–C bond-forming sequence has been developed using two distinct transition metal complexes. The sequence entails a double Pd-catalyzed allylic alkylation followed by a Ru-catalyzed ring-closing metathesis and a Pd-catalyzed Heck coupling. The use of various active methylene nucleophiles was examined with yields up to 76% (93% per C–C bond)

Iron-Catalyzed Intramolecular C(sp³)‑H Lactonization of Hydroxamate Derivatives Promoted by a 1,5-HAT

An iron-catalyzed lactonization reaction via intramolecular C(sp3)-H functionalization is described. The process employs easily accessible hydroxamate derivatives from which the noncommon insertion of the oxygen occurred through a 1,5-hydrogen atom transfer. A mixture of water and hexafluoroisopropanol as solvent appeared to be the key parameter of this transformation to reach a high selectivity and efficiency