Access to Unexplored 3D Chemical Space: cis‐Selective Arene Hydrogenation for the Synthesis of Saturated Cyclic Boronic Acids

A new class of saturated boron‐incorporated cyclic molecules has been synthesized employing an arene‐hydrogenation methodology. cis‐Selective hydrogenation of easily accessible, and biologically important molecules comprising benzoxaborole, benzoxaborinin, and benzoxaboripin derivatives is reported. Among the various catalysts tested, rhodium cyclic(alkyl)(amino)carbene [Rh‐CAAC] (1) pre‐catalyst revealed the best hydrogenation activity confirming turnover number up to 1400 with good to high diastereoselectivity. A broad range of functional groups was tolerated including sensitive substituents such as −F, −CF(3), and −silyl groups. The utility of the synthesized products was demonstrated by the recognition of diols and sugars under physiological conditions. These motifs can have a substantial importance in medicinal chemistry as they possess a three‐dimensional structure, are highly stable, soluble in water, form hydrogen bonds, and interact with diols and sugars.