Articles by Leonori Research Group Published in High-Profile Journals

Professor Daniele Leonori, Chair of Organic Chemistry III, and his research group have published two articles in the renowned journals “Science” and “Nature”.

 

An article by Professor Leonori’s research group, titled “Photoexcited nitroarenes for the oxidative cleavage of alkenes,” has recently been published in the prestigious journal Nature. The research is concerned with the oxidative cleavage of alkenes, an integral process that converts feedstock materials into high-value synthetic intermediates.

The most viable method to accomplish this in one chemical step is to use ozone, but this poses technical and safety challenges due to the explosive nature of ozonolysis products. The research group reports an alternative approach to the oxidative cleavage of alkenes using nitroarenes and irradiation with violet light. The group has demonstrated that photoexcited nitroarenes can serve as effective ozone surrogates. The resulting “N-doped” ozonides are safe to handle and lead to the corresponding carbonyl products under mild hydrolytic conditions. These properties enable the controlled cleavage of all types of alkenes in the presence of a wide range of commonly used organic functionalities.

Another research article by the team, “Halogen-atom and group transfer reactivity enabled by hydrogen tunneling,” appeared in the September 16 issue of Science.

Much of organic chemistry revolves around the bonding of carbon to atoms other than hydrogen. Occasionally, it is necessary to restore a carbon–hydrogen bond. The generation of carbon radicals via halogen atom and group transfer reactions is usually achieved using tin and silicon reagents that maximize the interplay of thermodynamic and kinetic effects. The researchers now demonstrate a distinct reactivity mode enabled by quantum mechanical tunneling. Experimental and computational studies unveiled a noncanonical pathway whereby a cyclohexadienyl radical undergoes concerted aromatization and halogen-atom or group abstraction through the reactivity of an effective H atom. This activation mechanism is seemingly thermodynamically and kinetically unfavorable but is rendered feasible through quantum tunneling.