Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

Abstract

Recent developments of stereoselective biocatalytic and chemocatalytic methods are discussed. The review provides a guide to the use of biocatalytic methods in the area of chemical synthesis with focused attention on retrosynthetic considerations and analysis. The transformations presented are organized according to bond disconnections and attendant synthetic methods. The review is expected to lead to better understanding of the characteristics and distinctions of the two complementary approaches. It depicts for researchers in bio- and chemocatalysis a road map of challenges and opportunities for the evolution (and at times revolution) in chemical synthesis.

Sequential Two‐Step Stereoselective Amination of Allylic Alcohols through the Combination of Laccases and Amine Transaminases

“…Biocatalytic methods have emerged as a sustainable solution for the synthesis of chiral amines by means of the single action of enzymes of several classes, including lipases, amine transaminases (ATAs), amine oxidases, amine dehydrogenases, imine reductases or reductive aminases, but, interestingly, great efforts have in recent years been devoted to the synthesis of chiral amines through chemo‐, photo‐ and multienzymatic approaches . As an example, the selective amination of racemic sec ‐alcohols through elegant cascades based on the combination of alcohol‐dehydrogenase‐catalysed oxidation to ketones with subsequent bioamination by using ATAs or amine dehydrogenases has been described.…”

Chemoenzymatic Total Synthesis of Deoxy‐, epi‐, and Podophyllotoxin and a Biocatalytic Kinetic Resolution of Dibenzylbutyrolactones

“…Aiming for an efficient synthesis by integrating biocatalysis [21] towards podophyllotoxin, the racemic yatein precursor (rac-2a)was prepared following aslightly modified literature procedure (Scheme 1a). [22] As imple switch to less polar solvents for the allylation step gave better diastereomeric ratios in our hands compared to the literature,and the target compound was obtained in good yields (82 %o verall yield).…”

Highly Diastereo‐ and Enantioselective Synthesis of Nitrile‐Substituted Cyclopropanes by Myoglobin‐Mediated Carbene Transfer Catalysis

“…This capability combined with the versatility of the cyano functional group, as exemplified by the transformation in Scheme 2, is expected to expand opportunities toward the exploitation of biocatalysis for asymmetric synthesis of pharmaceuticals and other high-value compounds. [21] …”