Chemoselective Hydrogenation of Aldehydes under Mild, Base-Free Conditions: Manganese Outperforms Rhenium.

ACS Catalysis
Mathias GlatzKarl Kirchner

Abstract

Several hydride Mn(I) and Re(I) PNP pincer complexes were applied as catalysts for the homogeneous chemoselective hydrogenation of aldehydes. Among these, [Mn(PNP-iPr)(CO)2(H)] was found to be one of the most efficient base metal catalysts for this process and represents a rare example which permits the selective hydrogenation of aldehydes in the presence of ketones and other reducible functionalities, such as C=C double bonds, esters, or nitriles. The reaction proceeds at room temperature under base-free conditions with catalyst loadings between 0.1 and 0.05 mol% and a hydrogen pressure of 50 bar (reaching TONs of up to 2000). A mechanism which involves an outer-sphere hydride transfer and reversible PNP ligand deprotonation/protonation is proposed. Analogous isoelectronic and isostructural Re(I) complexes were only poorly active.

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Citations

Apr 4, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Kasturi GanguliSabuj Kundu
Jan 3, 2019·Chemistry : a European Journal·Marc DevillardJarl Ivar van der Vlugt
Nov 18, 2018·ChemCatChem·Oriol Martínez-FerratéWalter Leitner
Nov 15, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Hanumanprasad PandiriBenudhar Punji
Mar 24, 2021·Organic Letters·Viktoriia ZubarMagnus Rueping
Jun 1, 2021·Organometallics·Stefan WeberKarl Kirchner
Oct 22, 2019·Journal of the American Chemical Society·Yujie WangQiang Liu
Jan 12, 2019·The Journal of Organic Chemistry·Milan K BarmanBiplab Maji
Jun 30, 2019·Journal of the American Chemical Society·Frederik FreitagRhett Kempe
Jun 5, 2018·Accounts of Chemical Research·Nikolaus Gorgas, Karl Kirchner
Apr 23, 2019·ACS Catalysis·Subrata ChakrabortyDavid Milstein
Aug 1, 2019·Journal of the American Chemical Society·Uttam Kumar DasDavid Milstein
Jan 15, 2022·Organic & Biomolecular Chemistry·Shreya MahatoTarun K Panda

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