Chemoenzymatic approaches to plant natural product inspired compounds

Abstract

Chemoenzymatic routes to plant natural products and analogues are described, highlighting the advantages of incorporating biocatalysis into synthetic strategies.

Peptide and Enzyme Catalysts Work in Concert in Stereoselective Cascade Reactions—Oxidation followed by Conjugate Addition

“…Nature evolved enzymes as powerful catalysts for the metabolism of living organisms, often as part of multi‐catalyst reaction networks [1–3] . Several enzymes are also useful for organic synthesis [4–8] . Over the past two decades, scientists developed efficient peptide catalysts for organic synthesis [9,10] .…”

“…[1][2][3] Several enzymes are also useful for organic synthesis. [4][5][6][7][8] Over the past two decades, scientists developed efficient peptide catalysts for organic synthesis. [9,10] Like enzymes, peptide catalysts consist of amino acids but have significantly lower molecular weight and operate in markedly different conditions (Scheme 1A).…”

The use of tyrosinases in a chemoenzymatic cascade as a peptide ligation strategy

“…[1][2][3][4] Protein engineering, especially enzyme mutagenesis, has also endowed biocatalysts with higher efficiencies and broader substrate acceptance for use in natural and unnatural product syntheses, enabling chemoenzymatic strategies to be more widely adopted. [4][5][6] Tyrosinases (TYRs) are Cu-dependent enzymes that convert L-tyrosine to melanin via oxidation of the monophenol to L-DOPA and then further oxidation. They are found widely in fungi, plants and animals and the catalytic mechanism has been well-studied, 7 as well as its importance in food, pharmaceutical and industrial applications.…”

“…1–4 Protein engineering, especially enzyme mutagenesis, has also endowed biocatalysts with higher efficiencies and broader substrate acceptance for use in natural and unnatural product syntheses, enabling chemoenzymatic strategies to be more widely adopted. 4–6…”

Current Progress in the Chemoenzymatic Synthesis of Natural Products

“…This research has produced advances in the variety and number of chemoenzymatic processes and increased their capabilities through scalability, multiple enzyme cascades, and flow processes. The importance of the chemoenzymatic synthesis of natural products can be seen in the explosion of recent syntheses and review articles highlighting their accomplishments [ 11 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. This report is organized by classification of molecule and aims to highlight the diversity and power of this field through selected chemoenzymatic syntheses of natural products from 2019–2022.…”