Catalytic Hydroxylation of Arylboronic Acids

Catalytic hydroxylation of arylboronic acids has emerged as a versatile strategy for the direct synthesis of phenols from readily available boron reagents. By exploiting the ipso-substitution of the boron moiety, these processes bypass traditional electrophilic aromatic substitution routes, offering mild conditions, broad functional-group tolerance and minimised waste. A variety of catalytic systems have been developed, including transition-metal complexes, organocatalysts and semiconductor photocatalysts, often in combination with terminal oxidants such as molecular oxygen, hydrogen peroxide or organic peroxides. Mechanistically, these methods proceed via activation of the boron substrate, generation of an oxygen radical or metal–oxo intermediate and subsequent C–O bond formation at the aryl centre. The resultant phenols find extensive applications in pharmaceuticals, agrochemicals and materials science, while the ambient-condition variants align with the principles of green chemistry by reducing energy consumption and hazardous by-products. Recent advances have focused on heterogeneous and light-driven protocols, sustainable oxidants and catalyst recyclability to enhance scalability and environmental compatibility.

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Catalytic Hydroxylation of Arylboronic Acids publication trend

The graph below shows the total number of articles in catalytic hydroxylation of arylboronic acids across all publications each year (not limited to Nature Index journals).

Technical terms

Arylboronic acid: An aromatic compound bearing a boronic acid group (–B(OH)₂) used as a versatile synthetic building block.

Ipso-hydroxylation: Direct replacement of a boron substituent on an aromatic ring by a hydroxyl group.

Chemoselectivity: Preferential reaction of one functional group over others present in a molecule.

Photocatalyst: A material or complex that absorbs light to drive chemical transformations via excited-state or radical pathways.

References

1. Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer. Chemical Science (2017).
2. A scalable and green one-minute synthesis of substituted phenols. RSC Advances (2020).
3. Linker-Assisted CdS-TiO2 Nanohybrids as Reusable Visible Light Photocatalysts for the Oxidative Hydroxylation of Arylboronic Acids. The Journal of Organic Chemistry (2023).