Chiral Phosphoric Acid-Catalyzed Remote Control of Axial Chirality at Boron-Carbon Bond

The previously elusive catalytic enantioselective construction of axially chiral B-aryl-1,2-azaborines with a C-B stereogenic axis has been realized through a chiral phosphoric acid-catalyzed desymmetrization strategy reported herein. The electrophilic aromatic substitution reaction of 3,5-disubsituted phenols with diazodicarboxamides could afford these axially chiral structures in good efficiency with excellent enantiocontrol. The efficient long-range stereochemical control is achieved by multiple well-defined H-bonding interactions between chiral phosphoric acid and both substrates. Meanwhile, the reaction duration could be markedly shortened with weakly acidic N-H in 1,2-azaborine acting as H-bond donor. The scalability of the reaction and facile cleavage of the N-N bond in the product further demonstrated the practicality of this method.

Automated summary

This study reports a new strategy for catalytic enantioselective construction of axially chiral B-aryl-1,2-azaborines, achieving efficient stereochemical control through multiple hydrogen bonding interactions. The reaction demonstrates high efficiency, excellent enantioselectivity, shortened reaction duration, and high practicality with scalable reaction and facile cleavage of N-N bond in the product.