<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The asymmetric, cis‐selective hydrogenation of 2, 3‐disubstituted quinoxalines employing chiral borane catalysts generated by the in situ hydroboration of chiral dienes with HB(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub> under mild reaction conditions is achieved with up to 96% ee.</p> </abstract>