Ruthenium-Catalyzed Direct Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones release_oszwydwturdhzabkvatqhd4u4i [as of editgroup_tgbxeg7nbvfsjfpeebwevr5csy]

by Subramanian Thiyagarajan, Chidambaram Gunanathan

Abstract

<jats:p>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.</jats:p><jats:p>1 Introduction</jats:p><jats:p>2 Catalytic Self- or Cross-Coupling of Alcohols and Selectivity Challenges</jats:p><jats:p>3 Recent Developments in the Synthesis of β-Disubstituted Ketones</jats:p><jats:p>4 Scope of Ruthenium-Catalyzed Cross-Couplings of Secondary Alcohols</jats:p><jats:p>5 Mechanistic Studies and Proposed Mechanism</jats:p><jats:p>6 Conclusion</jats:p>
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ISSN-L 0936-5214
Release Date 2019-08-13
Publisher Georg Thieme Verlag KG
Primary Language en (lookup)
Type  article-journal
Stage   published
Date   2019-08-13
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Unknown OA Status
Not in DOAJ
Not in ISSN ROAD
ISSN-L:  0936-5214
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