Manganese PNP-pincer catalyzed isomerization of allylic/homo-allylic alcohols to ketones – activity, selectivity, efficiency. Issue 22 (18th October 2019)

• Record Type: Journal Article
• Authors: Xia, Tian; Spiegelberg, Brian; Wei, Zhihong; Jiao, Haijun; Tin, Sergey; Hinze, Sandra; de Vries, Johannes G.
• Is Part Of: Catalysis science & technology. Volume 9:Issue 22(2019)
• Page Start: 6327
• Page End: 6334
• Publication Date: 2019-10-18
• Subjects: Catalysis -- Periodicals; 541.395
• DOI: 10.1039/c9cy01502g
• Languages: English
• ISSNs: 2044-4753

Abstract

Abstract : Manganese PNP pincer complexes are excellent catalysts for the isomerization of allylic alcohols to the ketones. The reaction proceeds via a dehydrogenation/hydrogenation mechanism as shown by DFT calculations and deuterium labelling. Abstract : We report the first manganese catalyzed isomerization of allylic alcohols to produce the corresponding carbonyl compounds. The ligand plays a decisive role in the efficiency of this reaction. Very high conversions could be obtained using a solvent-free reaction system. A detailed DFT study reveals a self-dehydrogenation/hydrogenation reaction mechanism which was verified by the isolation of the α, β-unsaturated ketone as intermediate and a deuterium labeling experiment. It also provided a rationale for the observed selectivity and the higher efficiency of phenyl over isopropyl substitution.