Science of Synthesis

Gröger, H.; Hummel, W., Science of Synthesis: Biocatalysis in Organic Synthesis, (2015) 3, 497.

The ability of palladium complexes to catalyze a broad spectrum of different types of transformations is widely known within organic synthesis. Palladium-catalyzed cross-coupling reactions are a landmark in this field;[‌33‌] see also Science of Synthesis: Cross Coupling and Heck-Type Reactions, Vol. 2 (Carbon—Heteroatom Cross Coupling and C—C Cross Coupling of Acidic C—H Nucleophiles). Today, palladium catalysis also represents a key technology for industrial applications, examples being the Heck and Suzuki reactions.[‌34‌] It is also noteworthy that palladium complexes are suitable for use in water in many cases, thus making them also interesting catalysts with respect to their combination with biotransformations toward one-pot, multistep processes. To start with an early example, the Williams group succeeded in coupling a palladium-catalyzed racemization of O-acylated allylic alcohols with an enzymatic hydrolysis, leading to the corresponding allylic alcohols.[‌35‌,‌36‌] This dynamic kinetic resolution proceeds in water and gives the desired alcohol products with both high conversion and enantioselectivities. For example, the synthesis of alcohol (S)-‌14‌ proceeds with 96% conversion and 96% ee when using a lipase from Pseudomonas fluorescens as the biocatalyst component in combination with bis(acetonitrile)dichloropalladium(II) for racemization of the ester ‌13‌ (‌Scheme 7‌).[‌35‌]

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References