Cross-Coupling Of Secondary Alcohols Research Articles

Divergent Synthesis of Alcohols and Ketones via Cross-Coupling of Secondary Alcohols under Manganese Catalysis.

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis of γ-disubstituted alcohols and β-disubstituted ketones is reported. Employing the well-defined Mn-MACHOPh as the catalyst, this novel protocol has a broad substrate scope with good functional group tolerance and affords a diverse library of valuable disubstituted alcohols and ketones in moderate to good yields. The strong influence of the reaction temperature on the selective formation of alcohol products was theorized in preliminary DFT studies. Studies have shown that the Gibbs free energy of the formation of alcohols is thermodynamically more favourable than corresponding ketones at a lower temperature.

Improved Process for the Palladium-Catalyzed C-O Cross-Coupling of Secondary Alcohols.

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.

Base-catalyzed cross coupling of secondary alcohols and aryl-aldehydes with concomitant oxidation of alcohols to ketones: An alternative route for synthesis of the Claisen-Schmidt condensation products

Abstract Base-catalyzed C–C cross coupling of secondary alcohols and aryl-aldehydes was achieved, when an alcoholic solution of an aryl-aldehyde was stirred under reflux for 45 h in the presence of a catalytic (20 mol%) amount of K 2 CO 3 . The consistent formation of α,α′- bis -(benzylidene) alkanones was obtained in moderate to good yields using various secondary alcohols and substituted aryl-aldehydes. Herein, α,α′- bis -(benzylidene)alkanones, which are the classical products of Claisen-Schmidt (cross aldol) condensation, have been synthesized via an alternative strategy using secondary alcohols. Bis -(benzylidene) alkanones are an integral part of various drug regimes and the production of bis -(benzylidene) alkanones without using any precious metal is a major outcome of the present reaction.