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Divergent Synthesis of Alcohols and Ketones via Cross-Coupling of Secondary Alcohols under Manganese Catalysis |
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| Authors: | Feixiang Sun Jiamin Huang Dr Zhihong Wei Prof?Dr Conghui Tang Prof?Dr Weiping Liu |
| Institution: | 1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Key Laboratory of Science and Technology of Eco-Textile, Ministry of Education, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620 P. R. China
These authors contributed equally to this work.;2. Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan, 030006 P. R. China;3. Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan, 430074 P. R. China;4. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Key Laboratory of Science and Technology of Eco-Textile, Ministry of Education, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620 P. R. China |
| Abstract: | 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. |
| Keywords: | Alcohols Borrowing Hydrogen Cross-Coupling Homogeneous Catalysis Manganese |