Supported copper on a diamide–diacid-bridged PMO: an efficient hybrid catalyst for the cascade oxidation of benzyl alcohols/Knoevenagel condensation

In this study, a novel periodic mesoporous organosilica (PMO) containing diamide–diacid bridges was conveniently prepared using ethylenediaminetetraacetic dianhydride to support Cu(ii) species and affording Cu@EDTAD-PMO nanoparticles efficiently.

Hydroxylamine-mediated C–C amination via an aza-hock rearrangement

Despite the widespread use of anilines, synthetic challenges to these targets still exist. Selectivity is often an issue, when using the traditional nitration-reduction sequence or more modern approaches, including arene C–H aminations catalyzed by transition metals, photosensitizers, or electrodes. Accordingly, there is still a need for general methods to rapidly, directly access specific isomers of substituted anilines. Here, we report a simple route towards the synthesis of such motifs starting from benzyl alcohols, which are converted to anilines by the use of arylsulfonyl hydroxylamines, via an aza-Hock rearrangement. Good to excellent yields are observed. The method is applicable to various benzyl alcohol surrogates (such as ethers, esters, and halides) as well as simple alkylarenes. Functionalizations of pharmaceutically relevant structures are feasible under the reaction conditions. Over ten amination reagents can be used, which facilitates the rapid assembly of a vast set of compounds.

Co-N-Si/AC Catalyst for Aerobic Oxidation of Benzyl Alcohols to Esters under Mild Conditions

A stable, earth-abundant, reusable cobalt-based heterogeneous catalyst is developed for the oxidative esterification of alcohols under ambient conditions, featuring broad substrate scope, providing good to excellent product yields. This protocol enables easy recyclability of the catalyst, measured up to five times without significant loss of efficiency. The active sites of Co-N-Si/AC are proposed to be Co-N species.