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Isomerization of Allylic Alcohols to Ketones Catalyzed by Well‐Defined Iron PNP Pincer Catalysts
Author(s) -
Xia Tian,
Wei Zhihong,
Spiegelberg Brian,
Jiao Haijun,
Hinze Sandra,
de Vries Johannes G.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705454
Subject(s) - isomerization , catalysis , chemistry , allylic rearrangement , ketone , alcohol , alkene , medicinal chemistry , hydride , amine gas treating , organic chemistry , hydrogen , photochemistry
[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.