The Baker–Venkataraman rearrangement refers to the transformation of ortho-acyloxyaryl ketones into the corresponding aryl β-diketones via a rearrangement reaction. It is named after chemists W. Baker and Krishnaswamy Venkataraman. The Baker–Venkataraman rearrangement is one of the most widely used methods for synthesizing chromones, flavones, and isoflavones.

Reagents: Base
Reactants: Ortho-acyloxyaryl ketones
Products: Aryl β-diketones
Reaction Type: Rearrangement reaction

Experimental Tips:

• The ortho-acyloxyaryl ketone undergoing the Baker–Venkataraman rearrangement must contain an α-hydrogen.

• Common solvents are aprotic solvents, such as THF.

• Frequently used bases include KOH, potassium tert-butoxide in DMSO, metallic sodium, KH or NaH, and pyridine.

Reaction Mechanism

Original References:

• Baker, W., J. Chem. Soc., 1933, 1381–1389.

• Mahal, H. S.; Venkataraman, K., J. Chem. Soc., 1934, 1767–1769.

Popular Citations:

• Directed ortho metalation - cross coupling links. Carbamoyl rendition of the Baker–Venkataraman rearrangement. Regiospecific route to substituted 4-hydroxycoumarins, Tetrahedron Letters, 1998, 39(28), 4995–4998.

• Mechanism and Application of Baker–Venkataraman O→C Acyl Migration Reactions, Synthesis, 2015, 47(02), 141–158.