Exploiting the Diels-Alder Reactions of Boron-Substituted Dienes and Dienophiles

NATALIA LABADIE; FEDERICO DEZOTTI; NOELIA S. MEDRÁN; JUAN M. RAMOS MARCHENA; SILVINA C. PELLEGRINET

Blacksburg, Virginia, USA

Congreso; 17th Boron Chemistry Meeting in the Americas; 2022

Comité organizador de BORAM 2022

The Diels-Alder (DA) cycloaddition is one of the most important organic reactions. A wide variety of unsaturated boron-substituted compounds have been used as DA dienes and dienophiles. In the past years, new variants of such transformations have been described. Our group has been devoted to expand the range of boron-substituted DA partners. Recently, we demonstrated that boron-substituted furans exhibit high reactivity and selectivity as Diels-Alder dienes. In particular, trifluoroborates stood out from their boronic ester and acid analogues, showing remarkable reactivity in the reactions with activated dienophiles such as maleic anhydride and N-phenylmaleimide. Also, we have developed different alternatives to tune the reactivity and the selectivity. In addition, we disclosed the potential of allenylboronic acid pinacol ester as a dienophile in [4 + 2] cycloadditions. The reaction with cyclopentadiene was found to be completely peri- and regioselective. The cycloadducts obtained in these reactions represent versatile scaffolds that can be submitted to diverse transformations to obtain a variety of chemical structures. The synthetic and mechanistic aspects of these reactions will be discussed.