Enantioselective hydrogenation using chiral complexes between atropisomeric diphosphines and ruthenium is a powerful tool for producing chiral compounds. Using a simple and straightforward in situ catalyst preparation, the conditions were optimized using molecular hydrogen for both academic and industrial purposes. This led to the best conditions and the lowest catalytic ratio required for the pressure used. Hydrogenation of various b-keto esters was efficiently performed at atmospheric and higher pressures, leading to the use of very low catalystsubstrate ratios up to 1/20,000. Asymmetric hydrogenations were used in key-steps towards the total synthesis of corynomycolic acid, Duloxetine and Fluoxetine.

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Thiamphenicol is a widely used antibiotic that exhibits activity against numerous Gram‐positive and Gram‐negative pathogens. Here, we describe the expedient synthesis of its four stereoisomers through a dynamic kinetic resolution that follows a ruthenium‐catalyzed asymmetric hydrogenation or a hydrogen transfer reaction as the key step.

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