Publications by authors named "Jonathan Medlock"

Electrosynthetic methods are crucial for a future sustainable transformation of the chemical industry. Being an integral part of many synthetic pathways, the electrification of hydrogenation reactions gained increasing interest in recent years. However, for the large-scale industrial application of electrochemical hydrogenations, low-resistance zero-gap electrolysers operating at high current densities and high substrate concentrations, ideally applying noble-metal-free catalyst systems, are required.

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Collaborations between academia and industry are vital for modern industrial research and development projects, combining the best of both worlds to develop sustainable chemical processes. Herein we summarize a number of successful cooperations between DSM Nutritional Products and Swiss academic institutions that have been carried out over approximately the past decade. A wide variety of reactions and processes have been investigated with experts located in Switzerland.

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A mild photocatalytic phenol oxygenation enabled by a continuous-flow photoreactor using visible light and pressurized air is described herein. Products for wide-ranging applications, including the synthesis of vitamins, were obtained in high yields by precisely controlling principal process parameters. The reactor design permits low organophotocatalyst loadings to generate singlet oxygen.

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A catalyst repurposing strategy based on a sequential aldol addition and transfer hydrogenation giving access to enantiomerically enriched α-hydroxy-γ-butyrolactones is described. The combination of a stereoselective, organocatalytic step, followed by an efficient catalytic aldehyde reduction induces an ensuing lactonization to provide enantioenriched butyrolactones from readily available starting materials. By capitalizing from the capacity of prolineamides to act as both an organocatalyst and a transfer hydrogenation ligand, catalyst repurposing allowed the development of an operationally simple, economic, and efficient sequential catalysis approach.

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The synthesis of hydroxenin monoacetate, a key intermediate in the manufacture of vitamin A, relies on the undesirable use of stoichiometric amounts of organic bases such as pyridine. Although the final product (vitamin A acetate) can be produced from hydroxenin diacetate, using the monoacetylated intermediate improves the overall process yield. Aiming to identify more efficient, environmentally benign alternatives, this work first studies the homogeneous acetylation reaction using pyridine.

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A novel protocol for microwave-assisted alkyne semi-hydrogenation under heterogeneous catalysis in a continuous flow reactor is reported herein. This challenging task has been accomplished using a multifaceted strategy which includes the ultrasound-assisted preparation of Pd nanoparticles (average 3.0 ± 0.

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The selective hydrogenation of the carbonyl functionality of α,β-unsaturated aldehydes and ketones is catalysed by ruthenium dichloride complexes bearing a tridentate NNS ligand as well as triphenylphosphine. The tridentate ligand backbone is flexible, as evidenced by the equilibrium observed in solution between the cis- and trans-isomers of the dichloride precatalysts, as well as crystal structures of several of these complexes. The complexes are activated by base in the presence of hydrogen and readily hydrogenate carbonyl functionalities under mild conditions.

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This paper reports the application of ultrasound in the semi-hydrogenation of alkynes over two novel Pd/Boehmite catalysts. The semi-hydrogenations of phenylacetylene, diphenylacetylene and 2-butyne-1,4-diol have either been investigated in an ultrasonic bath under atmospheric hydrogen pressure, or in an ultrasonic horn reactor under 0.1-0.

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The discovery of vitamins as essential factors in the diet was a scientific breakthrough that changed the world. Diseases such as scurvy, rickets, beriberi, and pellagra were recognized to be curable with an adequate diet. These diseases had been prevalent for thousands of years and had a dramatic impact on societies as well as on economic development.

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[reaction: see text] The use of three chiral 1,4-diamines in the [(diphosphine) RuCl(2) (diamine)] catalyst system is demonstrated in the hydrogenation of acetophenone. The use of a 1,4-diamine offers unique properties that allow tuning of the catalyst system. These include the first example of the use of a racemic diamine in combination with a chiral phosphine, which gives 95% ee in the hydrogenation of isobutyrophenone.

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