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Synlett 2019; 30(18): 2027-2034
DOI: 10.1055/s-0037-1611912
DOI: 10.1055/s-0037-1611912
synpacts
Ruthenium-Catalyzed Direct Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones
We thank SERB New Delhi (EMR/2016/002517), DAE, and NISER for financial support.Further Information
Publication History
Received: 17 June 2019
Accepted after revision: 01 August 2019
Publication Date:
13 August 2019 (online)
Abstract
The β-disubstituted ketone functionality is prevalent in biologically active compounds and in pharmaceuticals. A ruthenium-catalyzed direct synthesis of β-disubstituted ketones by cross-coupling of two different secondary alcohols is reported. This new protocol was applied to the synthesis of variety of β-disubstituted ketones from various cyclic, acyclic, symmetrical, and unsymmetrical secondary alcohols. An amine–amide metal–ligand cooperation in a Ru catalyst facilitates the activation and formation of covalent bonds in selective sequences to provide the products. Kinetic and deuterium-labeling experiments suggested that aliphatic alcohols oxidize faster than benzylic secondary alcohols. A plausible mechanism is proposed on the basis of mechanistic and kinetic studies. Water and H2 are the only byproducts from this selective cross-coupling of secondary alcohols.
1 Introduction
2 Catalytic Self- or Cross-Coupling of Alcohols and Selectivity Challenges
3 Recent Developments in the Synthesis of β-Disubstituted Ketones
4 Scope of Ruthenium-Catalyzed Cross-Couplings of Secondary Alcohols
5 Mechanistic Studies and Proposed Mechanism
6 Conclusion
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For reviews on borrowing-hydrogen methodology, see:
For reviews on acceptorless dehydrogenation of alcohols, see: