Base-free chemoselective transfer hydrogenation of nitroarenes to anilines with formic acid as hydrogen source by a reusable heterogeneous Pd/ZrP catalyst $(document).ready(function() { if (!$("html").hasClass("ie8")) { $.ajax({ url: "https://crossmark-cdn.crossref.org/widget/v2.0/widget.js", dataType: "script", cache: true }).done(function() { $(".crossmark-button").addClass("visible"); }); } });

Abstract

A highly efficient, chemoselective, environmentally-benign method is developed for the catalytic transfer hydrogenation (CTH) of nitroarenes using FA as a hydrogen source. Various supported Pd catalysts were examined for this transformation, and Pd supported ZrP (Pd/ZrP) proved to be the best catalyst for CTH of nitrobenzene. Applicability of the Pd/ZrP catalyst is also explored for hydrogenation of various substituted nitroarenes. The Pd/ZrP catalyst showed high specificity for hydrogenation of nitro groups even in the presence of other reducible functional groups such as –CC, –COOCH₃, and –CN. To investigate the reaction mechanism, a Hammett plot was obtained for CTH of p-substituted nitroarenes. The active site is thought to be in situ generated Pd(0) species as seen from XRD and TEM data. The Pd/ZrP catalyst is reusable at least up to 4 times while maintaining the same activity and selectivity. To the best of our knowledge, this is one of the best methodologies for CTH of nitroarenes under base-free conditions with high activity and chemoselectivity over heterogeneous Pd-based catalysts.