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Abstract
Catalytic reduction of a representative set of imines, both aldimines and ketimines, to amines has been studied using transfer hydrogenation from 1,4-dicyclohexadiene. Unusually, this has been achieved using s-block pre-catalysts, namely 1-metallo-2-tert-butyl- 1,2-dihydropyridines, 2-tBuC5H5NM, M(tBuDHP), where M = Li-Cs. Reactions have been monitored in C6D6 and tetrahydrofuran-d8 (THFd8). A definite trend is observed in catalyst efficiency with the heavier alkali metal tBuDHPs outperforming the lighter congeners. In general, Cs(tBuDHP) is the optimal pre-catalyst with, in the best cases, reactions producing quantitative yields of amines in minutes at room temperature using 5 mol% catalyst. Supporting the experimental study, Density Functional Theory (DFT) calculations have also been carried out which reveal that Cs has a pathway with a significantly lower rate determining step than the Li congener. In the postulated initiation pathways DHP can act as either a base or as a surrogate hydride.
Original language | English |
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Article number | e202304966 |
Number of pages | 10 |
Journal | Angewandte Chemie International Edition |
Volume | 62 |
Issue number | 27 |
Early online date | 3 May 2023 |
DOIs | |
Publication status | Published - 3 Jul 2023 |
Keywords
- alkali metal
- caesium
- catalysis
- dihydropyridine
- hydrogenation
- catalytic reduction
- experimental study
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Dive into the research topics of 'Alkali metal dihydropyridines in transfer hydrogenation catalysis of imines: amide basicity versus hydride surrogacy'. Together they form a unique fingerprint.-
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Bespoke Bimetallics for Chemical Cooperativity
EPSRC (Engineering and Physical Sciences Research Council)
1/09/19 → 31/08/22
Project: Research
Datasets
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Data for: "Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy"
MacDonald, P. A. (Contributor), Banerjee, S. (Contributor), van Teijlingen, A. (Contributor), Kennedy, A. (Contributor), Robertson, S. (Contributor), Tuttle, T. (Contributor) & Mulvey, R. (Creator), University of Strathclyde, 4 May 2023
DOI: 10.15129/197577c8-b28e-43b4-9ab4-badd48c084f7
Dataset