Staudt_2022_Mol.Catal_528_112464

Monoterpenes are secondary metabolites derived from plants and are represented by compounds of varied chemical structures and diverse pharmacological properties. These metabolites can be converted into a wide range of valuable chemicals, such as the correspondent esters, commonly applied in the food, pharmaceutical, and cosmetic industries. Monoterpene esters are commonly produced chemically, although this process presents different limitations, and aiming to overcome these limitations, biocatalysis can be presented as a valuable alternative. The present work aimed to report the state of art and advancement of the biocatalytic synthesis of monoterpene esters, going on deep in the knowledge of the biocatalysts from an evolutionary analysis point of view. A bibliometric study was performed on the platform Scopus regarding the biocatalytic acylation of monoterpene alcohols over time (1969-2021) to construct this review. From the literature data, it was obtained a broad range of hydrolases-type enzymes applied to the acylation of monoterpene alcohols, being the lipases responsible for more than 95% of the publications concerning primary (105 from 110 publications) and secondary (65 of 68 publications) monoterpene alcohols acylation reactions. The lipase was the only subclass of enzymes applied towards tertiary monoterpene alcohols. Furthermore, the lipases described were mainly obtained from fungi (79% (83 of 105 publications) of the reported biocatalysts towards primary alcohols, 70% (46 of 65 publications) for secondary alcohols, and 89% (8 of 9 publications) for tertiary alcohols), followed by bacteria, animals, and plants. To provide an overview of all putative hydrolases available in the sequence databases, a phylogenetic tree was constructed based on a blast with nine hydrolases (lipases from porcine pancreas, Candida rugosa, Rhizomucor miehei, Aspergillus niger, Pseudomonas sp., and Burkholderia cepacia; and the esterases from pig liver esterase, Mycobacterium smegmatis, and Pyrobaculum calidifontis), from which a final alignment with 5383 sequences was created and visualized with a phylogenetic tree. As for, this work provided and addressed an interesting evolutionary and perspective of the biocatalytic synthesis of monoterpene esters.