Isomerization of Allylic Alcohols to Ketones Catalyzed by Well‐Defined Iron PNP Pincer Catalysts. Issue 16 (16th January 2018)

• Record Type: Journal Article
• Authors: Xia, Tian; Wei, Zhihong; Spiegelberg, Brian; Jiao, Haijun; Hinze, Sandra; de Vries, Johannes G.
• Is Part Of: Chemistry. Volume 24:Issue 16(2018)
• Page Start: 4043
• Page End: 4049
• Publication Date: 2018-01-16
• Subjects: allylic alcohols -- density functional calculations -- iron catalyst -- isomerization -- ketones -- pincer ligands; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201705454
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: [Fe(PNP)(CO)HCl] (PNP=di‐(2‐diisopropylphosphanyl‐ethyl)amine), activated in situ with KO t Bu, is a highly active catalyst for the isomerization of allylic alcohols to ketones without an external hydrogen supply. High reaction rates were obtained at 80 °C, but the catalyst is also sufficiently active at room temperature with most substrates. The reaction follows a self‐hydrogen‐borrowing mechanism, as verified by DFT calculations. An alternative isomerization through alkene insertion and β‐hydride elimination could be excluded on the basis of a much higher barrier. In alcoholic solvents, the ketone product is further reduced to the saturated alcohol. Abstract : A borrowing pincer : The isomerization of non‐activated allylic alcohols to ketones catalyzed by an iron(II) PNP pincer complex (see graphic) is reported. High reaction rates have been achieved, even at room temperature. A self‐borrowing hydrogen mechanism has been established on the basis of DFT calculations.