Abstract

During the last decade, the combination of different metal- and bio-catalyzed organic reactions in aqueous media has permitted the flourishing of a variety of one-pot asymmetric multi-catalytic reactions devoted to the construction of enantiopure and high added-value chemicals under mild reaction conditions (usually room temperature) and in the presence of air. Herein, a comprehensive account of the state-of-the-art in the development of catalytic networks by combining metallic and biological catalysts in aqueous media (the natural environment of enzymes) is presented. Among others, the combination of metal-catalyzed isomerizations, cycloadditions, hydrations, olefin metathesis, oxidations, C-C cross-coupling and hydrogenation reactions, with several biocatalyzed transformations of organic groups (enzymatic reduction, epoxidation, halogenation or ester hydrolysis), are discussed.

Highlights

  • Challenges faced by today’s synthetic organic chemists when trying to access highly-functionalized small molecules are evolving rapidly due to the new safety and economic needs imposed by our society [1]

  • Recent years have seen an impressive advance in multi-enzymatic systems of remarkable complexity [7,8,9,10], which try to emulate Nature, as living organisms use a great number of enzymatic cascades employing the same reaction media

  • Metal-catalyzed alkene metathesis is one of the most efficient tools for accomplishing catalyst the optimization of the reaction hasnew led to thethe formation of newbased

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Summary

Introduction

Challenges faced by today’s synthetic organic chemists when trying to access highly-functionalized small molecules are evolving rapidly due to the new safety and economic needs imposed by our society [1]. Ru(IV)‐catalyzed isomerization of the desired allylic alcohol was completed in the buffer be solution, exerted by the enzymatic system on the metal This drawback could be circumvented just by adopting one‐pot/two‐step methodology. Ru(IV)-catalyzed isomerization ofco‐factor the desired alcohol was completed in thetobuffer solution, the corresponding ω‐TA and itswithout pyridoxal were added the reaction enantiopure saturated amines, the(PLP, needallylic for any halfway isolation or purification steps This methodology enabled transforming racemic allylic alcohols into the corresponding themedia. Combination of this subrogated hydration processenantiomers with a concomitant promoted excellent enantiomeric excesses for both possible after 24 hbioreduction of reaction At this point, it is important to note that the reaction media coming from the metal-catalyzed reaction by KREDs allowed us to obtain thethat corresponding.

One‐pot synthesis of enantiopure
Metal‐Catalyzed
Combination
II catalysts were employed air-tolerant
16. Decarboxylation
24.24. Enzymatic
Combination of Metal-Catalyzed withisEnzymatic
Findings
Conclusions
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