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Jonah B. Eisenberg ; Kwanpyung Lee ; Xin Yuan , et al. JACS,2024,146(22):15309-15319. DOI: 10.1021/jacs.4c03032 PubMed ID: 38771660
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Abstract: The hydrogenolysis or hydrodeoxygenation of a carbonyl group, where the C═O group is converted to a CH2 group, is of significant interest in a variety of fields. A challenge in electrochemically achieving hydrogenolysis of a carbonyl group with high selectivity is that electrochemical hydrogenation of a carbonyl group, which converts the C═O group to an alcohol group (CH-OH), is demonstrated not to be the initial step of hydrogenolysis. Instead, hydrogenation and hydrogenolysis occur in parallel, and they are competing reactions. This means that although both hydrogenolysis and hydrogenation require adding H atoms to the carbonyl group, they involve different intermediates formed on the electrode surface. Thus, revealing the difference in intermediates, transition states, and kinetic barriers for hydrogenolysis and hydrogenation pathways is the key to understanding and controlling hydrogenolysis/hydrogenation selectivity of carbonyl compounds. In this study, we aimed to identify features of reactant molecules that can affect their hydrogenolysis/hydrogenation selectivity on a Zn electrode that was previously shown to promote hydrogenolysis over hydrogenation. In particular, we examined the electrochemical reduction of para-substituted benzaldehyde compounds with substituent groups having different electron donating/withdrawing abilities. Our results show a strikingly systematic impact of the substituent group where a stronger electron-donating group promotes hydrogenolysis and a stronger electron-withdrawing group promotes hydrogenation. These experimental results are presented with computational results explaining the substituent effects on the thermodynamics and kinetics of electrochemical hydrogenolysis and hydrogenation pathways, which also provide critically needed information and insights into the transition states involved with these pathways.
Purchased from AmBeed: 874-89-5
CAS No. : | 874-89-5 | MDL No. : | MFCD00870633 |
Formula : | C8H7NO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | XAASLEJRGFPHEV-UHFFFAOYSA-N |
M.W : | 133.15 | Pubchem ID : | 160549 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302+H312+H332-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; lithium aluminium tetrahydride; In tetrahydrofuran; methanol; | (i) 4-Aminomethylbenzyl alcohol preparation 4-(Hydroxymethyl)benzonitrile (1.0 g, 7.5 mmol) dissolved in dry tetrahydrofuran (20 ml) was added slowly into a suspension of LiAlH4 (866 mg, 22.8 mmol) in tetrahydrofuran (20 ml) at room temperature. Foaming with bubble formation was observed while stirring. The light yellow-green suspension was refluxed under N2 overnight. After cooling down to room temperature, methanol (5 ml) was added to the suspension to quench the reaction. The suspension was foaming while stirring and cooling down in ice-bath. When no more bubble formation was observed, sodium hydroxide (20percent, 15 ml) solution was added into the suspension. The solution became colorless while white precipitate was observed. The solution was concentrated in vacuo and the residue was suction filtered. The solid was repeatedly washed with methylene dichloride. The filtrate was combined and washed with water. The organic phase was separated and concentrated by a rotavapor. White solid was obtained as product (1.0 g, yield 98percent). The product underwent prolonged drying in vacuo to remove residue solvent before the next step reaction. 1H-NMR (CDCl3): delta7.31 (m, 4H), 4.67 (s, 2H), 3.85 (s, 2H), 1.76 (s broad, 3H); 13C-NMR (CDCl3): delta142.7, 139.9, 127.5, 127.5, 65.2, 46.4 4-Boc-aminomethylbenzyl alcohol |
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