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Updated: Dec 17, 2025

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Improved Process for the Palladium-Catalyzed C-O Cross-Coupling of Secondary Alcohols
Hong Zhang1, Paula Ruiz-Castillo1, Alexander W Schuppe1
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Abstract:
An improved protocol for the Pd-catalyzed C-O cross-coupling of secondary alcohols is described. The use of biaryl phosphine L2 as the ligand was key to achieving efficient cross-coupling of (hetero)aryl chlorides with only a 20% molar excess of the alcohol. Additionally, we observed an unusual reactivity difference between an electron-rich aryl bromide and the analogous aryl chloride, and deuterium-labeling suggested that currently unidentified pathways for reduction play an important role in explaining this disparity.
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