Chemoselective formation of cyclo-aliphatic and cyclo-olefinic 1,3-diols pressure hydrogenation of potentially biobased platform molecules using Knölker-type catalysts

• Published in: Dalton transactions : an international journal of inorganic chemistry 2021-07, Vol.5 (29), p.112-1112
• Main Authors: van Slagmaat, Christian A. M. R, Faber, Teresa, Chou, Khi Chhay, Schwalb Freire, Alfonso J, Hadavi, Darya, Han, Peiliang, Quaedflieg, Peter J. L. M, Verzijl, Gerard K. M, Alsters, Paul L, De Wildeman, Stefaan M. A
• Format: Article
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt01252e

The hydrogenative conversions of the biobased platform molecules 4-hydroxycyclopent-2-enone and cyclopentane-1,3-dione to their corresponding 1,3-diols are established using a pre-activated Knölker-type iron catalyst. The catalyst exhibits a high selectivity for ketone reduction, and does not induce dehydration. Moreover, by using different substituents of the ligand, the cis - trans ratio of the products can be affected substantially. A decent compatibility of this catalytic system with various structurally related substrates is demonstrated. Hemicellulose-derived five-membered cyclic ketones are strategic precursors for sustainable 1,3-diol building blocks, and bifunctional iron catalysts provide unprecedented chemoselectivity in hydrogenation toward aliphatic and olefinic structures.