Biosynthetic pathway of aliphatic formates via a Baeyer–Villiger oxidation in mechanism present in astigmatid mites

Abstract

Astigmatid mites depend on bioactive glandular secretions, pheromones, and defensive agents to mediate intra- and interspecies interactions. Aliphatic formates, such as (Z,Z)-8,11-heptadecadienyl formate (8,11-F17) and (Z)-8-heptadecenyl formate (8-F17), are rarely encountered natural products that are abundant inSancassaniasp. Sasagawa (Acari: Acaridae) mite secretions. Linoleic acid and oleic acid are predicted as key intermediates in the synthesis of the closely related aliphatic formates. To gain insight in this biosynthetic pathway, acarid mite feeding experiments were conducted using13C-labeled precursors to precisely track incorporation. Analyses using13C NMR spectroscopy demonstrated that the13C-labeling pattern of the precursors was detectable on formates in exocrine secretions and likewise on fatty acids in total lipid pools. Curiously, the results demonstrated that the formates were biosynthesized without the dehomologation of corresponding fatty acids. Careful examination of the mass spectra from labeling experiments revealed that the carbonyl carbon of the formates is originally derived from the C-1 position of the fatty acids. Consistent with a Baeyer–Villiger oxidation reaction, labeling studies support the insertion of an oxygen atom between the carbonyl group and carbon chain. Empirical data support the existence of a Baeyer–Villiger monooxygenase responsible for the catalyzation of the Baeyer–Villiger oxidation. The predicted existence of a Baeyer–Villiger monooxygenase capable of converting aliphatic aldehydes to formates represents an exciting opportunity to expand the enzymatic toolbox available for controlled biochemical synthesis.

Controlling the Regioselectivity of Baeyer–Villiger Monooxygenases by Mutation of Active‐Site Residues

“…However, the formation of the abnormal product by BVMOs was reported for a number of reactions, such as the conversions of chiral nitrilolactones, terpenones, β‐amino ketones, β‐hydroxy ketones, and bicyclic ketones . Divergent regioselectivities for different BVMOs have also been observed for the conversion of aldehydes into formates or carboxylic acids and long‐chain ketocarboxylic acids . Thus, understanding how regioselectivity can be controlled is necessary for the development of tailored BVMOs for a variety of applications.…”

Diterpenoids and Sesquiterpenoids from Syzygium fluviatile

“…Consequently, the structure of 1 was established as cassipouryl formate. The biosynthetic pathway of diterpenoids 1−4 was discussed as the reference [10] (Figure 3). The known compounds were assigned as cassipourol (2) [9], 4',5'-dehydrodiodictyonema (3) [11], acetyl incensole (4) [12], aromadendrane-4β,10β-diol (5) [13], (-)-globulol (6) [14], spathulenol (7) [15], 3β,6β,8α,10β-tetramethylwiddrane-2(3)-en-10α-ol (8) [16], and α-cadinol (9) [17] according to their NMR and MS data as well as the comparison with the reported values.…”

Molecular evolutionary trends and biosynthesis pathways in the Oribatida revealed by the genome ofArchegozetes longisetosus

“…There is, however, no evidence of nerol in the traces of any oribatid or astigmatid mite species (30,88,184). Aliphatic non-terpene formats in Astigmata are synthesized by dehomologation and generation of a onecarbon-shorter primary alcohol from an aldehyde via hydrolysis of formate in a biological Baeyer-Villiger oxidation catalyzed by a novel, uncharacterized enzyme (226). A similar reaction to synthesize terpene formates is unlikely, as the terpenoid backbone would be shortened by onecarbon and this does not happen in any possible scenario.…”