Strategic replacement of protons with fluorine atoms or functional groups fluorine-containing fragments has proven a powerful strategy to optimize the activity therapeutic compounds. For this reason, synthetic chemistry organofluorides been subject intense development and innovation for many years. By comparison, literature on biocatalysis still makes slim chapter. Herein we introduce S-adenosylmethionine (SAM) dependent methyltransferases as new tool production fluorinated We demonstrate...

Pyrrolizidine alkaloid (PA) poisoning is well-known because of the intake PA-containing plant-derived natural products and PA-contaminated foodstuffs. Based on different structures necine bases, PAs are classified into three types: retronecine, otonecine, platynecine type. The former two type possessing an unsaturated base with a 1,2-double bond hepatotoxic due to P450-mediated metabolic activation generate reactive pyrrolic ester, which interacts cellular macromolecules leading toxicity....

Abstract Biosynthesis of N ‐α‐trimethyl‐2‐thiohistidine (ergothioneine) is a frequent trait in cyanobacteria. This sulfur compound may provide essential relief from oxidative stress related to oxygenic photosynthesis. The central steps ergothioneine biosynthesis are catalyzed by histidine methyltransferase and an iron‐dependent sulfoxide synthase. In this report, we present evidence that some cyanobacteria recruited adapted synthase different biosynthetic pathway make ergothioneine....

Abstract This report describes a modular enzyme‐catalyzed cascade reaction that transforms l ‐ or d ‐α‐amino acids to β‐methyl‐α‐amino acids. In this process an α‐amino acid transaminase, α‐keto methyltransferase, and halide methyltransferase cooperate in two orthogonal cycles mediate product formation regeneration of the cofactor pyridoxal‐5′‐phosphate co‐substrate S‐adenosylmethionine. The only stoichiometric reagents consumed are unprotected methyl iodide.

Oxyfunctionalization of abundant carboxylic acids represents a direct approach to synthesizing α-hydroxy acids, which are valuable intermediates various active pharmaceutical ingredients. Although ideal, the transformation is yet be accomplished. Herein, enantiocomplementary C(sp3)–H oxyfunctionalization for synthesis was realized by cooperative strategy substrate engineering, homologue screening and protein engineering α-ketoglutarate-dependent nonheme iron aryloxyalkanoate dioxygenases....

Aldolases are powerful C-C bond-forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, promising scalability. Stereodivergent engineering aldolases to tune the selectivity stereoisomers chiral molecules is highly desirable but has rarely been reported. This study documented semirational decarboxylative aldolase UstD with focused rational iterative site-specific mutagenesis (FRISM) strategy perform a reaction dione...

Aldolases are powerful C−C bond‐forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, promising scalability. Stereodivergent engineering aldolases to tune the selectivity stereoisomers chiral molecules is highly desirable but has rarely been reported. This study documented semirational decarboxylative aldolase UstD with focused rational iterative site‐specific mutagenesis (FRISM) strategy perform a reaction dione...

Genetic code expansion has significantly enhanced the diversity and functionality of proteins in biological world, leading to a wide range applications catalysis, biology, medicine. Despite extraordinary advances genetic over past years, availability cost noncanonical amino acids (ncAAs) remain one major obstacles, particularly for large-scale industrial production. In situ biosynthesis ncAAs from commercially available precursors offers promising solution this challenge, yet only few...

ABSTRACT Bacteria use various endogenous antioxidants for protection against oxidative stress associated with environmental survival or host infection. Although glutathione (GSH) is the most abundant and widely used antioxidant in Proteobacteria, ergothioneine (EGT) another microbial antioxidant, mainly produced by fungi Actinobacteria. The Burkholderia genus found diverse niches. We observed that gene homologs required synthesis of EGT are distributed throughout genus. By generating...

Dimethylsulfoniopropionate (DMSP) is one of the most abundant sulfur metabolites in marine environments. The biosynthesis DMSP and its degradation to dimethylsulfide are important links planetary cycle. Herein, first complete description a biosynthetic pathway provided by vitro reconstitution four enzymes from Streptomyces mobaraensis. isolation S. mobaraensis cells grown at high salinity confirmed that this actinobacterium indeed DMSP-producing organism. described follows same route as...

The development of mild, efficient, and enantioselective methods for preparing chiral building blocks from simple, renewable carbon units has been a long-term goal the sustainable chemical industry. Mandelate derivatives are valuable pharmaceutical intermediates resolving agents, but their manufacture relies heavily on highly toxic cyanide. Herein, we report (S)-4-hydroxymandelate synthase (HmaS)-centered biocatalytic cascades synthesis mandelates benzaldehydes glycine. We show that HmaS can...

Abstract This report describes a modular enzyme‐catalyzed cascade reaction that transforms l ‐ or d ‐α‐amino acids to β‐methyl‐α‐amino acids. In this process an α‐amino acid transaminase, α‐keto methyltransferase, and halide methyltransferase cooperate in two orthogonal cycles mediate product formation regeneration of the cofactor pyridoxal‐5′‐phosphate co‐substrate S‐adenosylmethionine. The only stoichiometric reagents consumed are unprotected methyl iodide.

Abstract C( sp 3 )−H oxyfunctionalization, the insertion of an O‐atom into bonds, streamlines synthesis complex molecules from easily accessible precursors and represents one most challenging tasks in organic chemistry with regard to site stereoselectivity. Biocatalytic oxyfunctionalization has potential overcome limitations inherent small‐molecule‐mediated approaches by delivering catalyst‐controlled selectivity. Through enzyme repurposing activity profiling natural variants, we have...

Nine new, uncommon humulane-type sesquiterpenoids (1, 2, 4, 6–11), together with two known derivatives, were isolated from extracts of the plant Pilea cavaleriei subsp. crenata. The structures these compounds fully elucidated by extensive analyses spectroscopic data (MS, 1D- and 2D-NMR), use Mosher method, X-ray crystallographic analysis, in combination chemical conversions. An ene reaction was discovered during transformations, which might provide an explanation for wide distribution...

Abstract Dimethylsulfoniopropionate (DMSP) is one of the most abundant sulfur metabolites in marine environments. The biosynthesis DMSP and its degradation to dimethylsulfide are important links planetary cycle. Herein, first complete description a biosynthetic pathway provided by vitro reconstitution four enzymes from Streptomyces mobaraensis . isolation S. cells grown at high salinity confirmed that this actinobacterium indeed DMSP‐producing organism. described follows same route as...

Abstract Sulfoxide synthases are non‐heme iron enzymes that participate in the biosynthesis of thiohistidines, such as ergothioneine and ovothiol A. The sulfoxide synthase EgtB from Chloracidobacterium thermophilum ( Cth EgtB) catalyzes oxidative coupling between side chains N ‐α‐trimethyl histidine (TMH) cysteine (Cys) a reaction entails complete reduction molecular oxygen, carbon–sulfur (C−S) sulfur–oxygen (S−O) bond formation well carbon–hydrogen (C−H) cleavage. In this report, we show...

Abstract Aldolases are powerful C−C bond‐forming enzymes with high stereoselectivity and broad substrate scope in biocatalysis, but their ability to stereoselectively construct tertiary alcohols has not been fully explored. Herein, we demonstrate that vicinal diones α‐keto esters electrophiles can be accepted by both natural computationally designed aldolases via various catalytic mechanisms. This method allows for the efficient asymmetric synthesis of small molecules alcohols, including...

Abstract Strategic replacement of protons with fluorine atoms or functional groups fluorine‐containing fragments has proven a powerful strategy to optimize the activity therapeutic compounds. For this reason, synthetic chemistry organofluorides been subject intense development and innovation for many years. By comparison, literature on biocatalysis still makes slim chapter. Herein we introduce S ‐adenosylmethionine (SAM) dependent methyltransferases as new tool production fluorinated We...

Noncanonical amino acids (ncAAs) containing tertiary alcohols are valuable as precursors of natural products and active pharmaceutical ingredients. However, the assembly such ncAA scaffolds from simple material by C-C bond formation remains a challenging task due to presence multiple stereocenters large steric hindrance. In this study, we present novel solution problem through highly selective enzymatic decarboxylative aldol addition. This method allows for streamlined multifunctionalized...

A feasible and sustainable approach for stereo-selective synthesis of non-canonical γ-hydroxy-α-amino acids from l -aspartic acid different aldehydes has been developed.

Abstract Deuterated hydroxyl acids and amino have been widely utilized in life science, biochemistry drug development. Site‐selective stereoselective synthesis of deuterated remains a significant challenge. Here, we report the development robust whole‐cell‐based chemoenzymatic platform for from off‐the‐shelf aldehydes high yields with excellent selectivities levels deuteration. The delivers products diverse scaffolds deuteration patterns, as well broad scopes both aromatic aliphatic side...

Abstract isolation and structure elucidation of nine new, uncommon humulane‐type sesquiterpenoids

Correction for ‘Stereo-selective synthesis of non-canonical γ-hydroxy-α-amino acids by enzymatic carbon–carbon bond formation’ Rui Zhang et al. , Catal. Sci. Technol. 2021, 11 7380–7385, https://doi.org/10.1039/D1CY00955A.