Biosynthesis of the Antifungal Polyhydroxy-Polyketide Acrophialocinol

Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 1036 - 1041

Published: Jan. 22, 2025

Bioactivity-guided isolation identified the main antifungal compounds produced by Acrophialophora levis as new polyhydroxy-polyketides acrophialocinol (1) and acrophialocin (2). Their biosynthesis was elucidated heterologous reconstitution in Aspergillus oryzae involves an α-ketoglutarate-dependent dioxygenase-catalyzed α-hydroxylation, resulting formation of a tertiary alcohol that is indispensable for activity. Furthermore, self-resistance toward mediated conserved RTA1-like protein encoded acr biosynthetic gene cluster.

Language: Английский

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%V_Bur index and steric maps: from predictive catalysis to machine learning

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 853 - 882

Published: Dec. 19, 2023

Steric indices are parameters used in chemistry to describe the spatial arrangement of atoms or groups molecules.

Language: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

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A chiral hydrogen atom abstraction catalyst for the enantioselective epimerization of meso -diols

Science, Journal Year: 2024, Volume and Issue: 386(6717), P. 42 - 49

Published: Oct. 3, 2024

Hydrogen atom abstraction is an important elementary chemical process but very difficult to carry out enantioselectively. We have developed catalysts, readily derived from the Cinchona alkaloid family of natural products, which can achieve this by virtue their chiral amine structure. The catalyst, following single-electron oxidation, desymmetrizes

Language: Английский

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Catalytic asymmetric oxidative coupling between C(sp3)–H bonds and carboxylic acids

Published: Aug. 13, 2024

Direct enantioselective functionalization of C(sp3)–H bonds in organic molecules could fundamentally transform the synthesis chiral molecules. In particular, oxidation these would dramatically change production alcohols and esters, which are prevalent natural products, pharmaceuticals, fine chemicals. Remarkable advances have been made construction carbon-carbon carbon-nitrogen through bond functionalization. However, direct formation carbon-oxygen from remains a considerable challenge. We herein report highly oxidative coupling with carboxylic acids using molecular copper catalyst activated by blue light. The method applies to allylic propargyl C–H more importantly employs various as oxygenating agents. By this method, we successfully synthesized range esters directly readily available alkenes alkynes, greatly simplifying related alcohols.

Language: Английский

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Bioinspired Non‐Heme Mn Catalysts for Regio‐ and Stereoselective Oxyfunctionalizations with H₂O₂

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(66)

Published: Aug. 29, 2023

Abstract In recent years, metalloenzymes‐mediated highly selective oxidations of organic substrates under mild conditions have been inspiration for developing synthetic bioinspired catalyst systems, capable conducting such processes in the laboratory (and, future, industry), relying on easy‐to‐handle and environmentally benign oxidants as H 2 O . To date, non‐heme manganese complexes with chiral bis ‐amino‐ ‐pyridylmethyl structurally related ligands are considered possessing highest potential, having demonstrated ability to mediate a variety chemo‐ stereoselective oxidative transformations, epoxidations, C(sp 3 )‐H hydroxylations ketonizations, desymmetrizations, kinetic resolutions, etc. Furthermore, past few years Mn based catalysts become major platform studies focused getting insight into molecular mechanisms oxidant activation (stereo)selective oxygen transfer, testing non‐traditional hydroperoxide oxidants, engineering catalytic sites enzyme‐like substrate recognition‐based selectivity, exploration regioselectivity trends oxidation biologically active natural origin. This contribution summarizes progress catalyzed C‐H oxygenative transformations substrates, achieved essentially 5 (late 2018–2023).

Language: Английский

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Understanding Catalytic Enantioselective C–H Bond Oxidation at Nonactivated Methylenes Through Predictive Statistical Modeling Analysis

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2110 - 2123

Published: Jan. 22, 2025

Enantioselective C(sp3)-H bond oxidation is a powerful strategy for installing functionality in rich molecules. Site- and enantioselective of strong C-H bonds monosubstituted cyclohexanes with hydrogen peroxide catalyzed by aminopyridine manganese catalysts combination alkanoic acids has been recently described. Mechanistic uncertainties nonobvious enantioselectivity trends challenge development the full potential this reaction as synthetic tool. Herein, we apply predictive statistical analysis to identify mechanistically informative correlations that provide valuable understanding will guide future optimization reactions.

Language: Английский

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Site‐Selective Distal C(sp3)–H Bromination of Aliphatic Amines as a Gateway for Forging Nitrogen‐Containing sp3 Architectures

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 21, 2024

Herein, we disclose a new strategy that rapidly and reliably incorporates bromine atoms at distal, secondary C(sp

Language: Английский

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In situ insertion of one or two types of hydroxy-rich noncanonical amino acids into one protein

Process Biochemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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Rational Design of the Spatial Effect in a Fe(II)/α‐Ketoglutarate‐Dependent Dioxygenase Reverses the Regioselectivity of C(sp³)−H Bond Hydroxylation in Aliphatic Amino Acids

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 25, 2024

Abstract The hydroxylation of remote C( sp 3 )−H bonds in aliphatic amino acids yields crucial precursors for the synthesis high‐value compounds. However, accurate regulation regioselectivity continues to be a common challenge chemosynthesis and biosynthesis. In this study, Fe(II)/α‐ketoglutarate‐dependent dioxygenase from Bacillus subtilis (BlAH) was mined found catalyze at γ δ sites acids. Crystal structure analysis, molecular dynamics simulations, quantum chemical calculations revealed that regulated by spatial effect BlAH. Based on these results, BlAH reconstructed stabilize transition state site acids, thereby successfully reversing site. For example, L‐Homoleucine ( 5 ) reversed (1 : 12) (>99 1). present study not only expands toolbox biocatalysts regioselective functionalization bonds, but also provides theoretical guidance precision‐driven modification similarly complex molecules.

Language: Английский

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