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 grou...

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Published inAngewandte Chemie International Edition Vol. 62; no. 26; pp. e202303433 - n/a
Main Authors Sun, Feixiang, Huang, Jiamin, Wei, Zhihong, Tang, Conghui, Liu, Weiping
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 26.06.2023
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Alcohols
Borrowing Hydrogen
Catalysis
Catalysts
Chemistry
Chemistry, Multidisciplinary
Cross coupling
Divergence
Free energy
Functional groups
Gibbs free energy
Homogeneous Catalysis
Ketones
Manganese
Physical Sciences
Science & Technology
Substrates
Synthesis
Homogeneous Catalysis
COMPLEXES
Alcohols
Borrowing Hydrogen
METALS
BETA-ALKYLATION
AMINES
NITRILES
ALPHA-ALKYLATION
Cross-Coupling
LIGAND
ACCESS
Manganese
C-H
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Summary: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. A manganese‐catalyzed cross‐coupling of two secondary alcohols in a divergent synthesis of either γ‐disubstituted alcohols or β‐disubstituted ketones is herein reported. A wide range of different alcohols could undergo the cross‐coupling process smoothly and furnish the corresponding products by using the same catalyst, with overall moderate to good yields.
Bibliography:These authors contributed equally to this work.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202303433