Visible-Light-Induced Imine Hydrogenation Catalyzed by Thioxanthone-TfOH Complex

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Amino compounds are important molecules, commonly found in nature and widely applied industrial production. Recently, photocatalysis has been discovered as an efficient method to synthesize amino by promoting imine hydrogenation. In this work, a strategy of hydrogenation catalyzed 2e– consecutive photoinduced electron transfer (ConPET) process thioxanthone-TfOH complex (9-HTXTF) was thoroughly investigated with its reaction conditions optimized, substrate scope examined, mechanism elucidated, which provides for synthesizing compounds.

Language: Английский

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Imine Synthesis by Engineered d-Amino Acid Oxidase from Porcine Kidney

ACS Omega, Journal Year: 2025, Volume and Issue: 10(2), P. 2212 - 2221

Published: Jan. 10, 2025

Various symmetric and asymmetric imines were synthesized using the novel amine oxidase, obtained as variants of d-amino acid oxidase (pkDAO) from porcine kidney (Y228L/R283G) (I230A/R283G). Active primary produced intermediates in oxidation methylbenzylamine (MBA) derivatives trapped by aliphatic, aromatic amines diamines nucleophiles forming new imines. (R)-Fluoro-MBA was best substrate for imine synthesis, providing almost stoichiometric conversion (100 mM) achieving nearly 100% yield. Several (R)-MBA used substrates, corresponding synthesized. The turnover number N-benzylidenebenzylamine synthesis benzylamine calculated to be 1.61 × 105 (number moles reactant consumed per mole catalyst/h), which is more than 103 higher metal-, photo-, organo-catalysts reported so far. diastereomers bis(1-phenylethyl)amine, reduced products (R)-MBA, identified a mixture 84.9% (R,R)-bis(1-phenylethyl)amine 15.1% (R,S)-bis(1-phenylethyl)amine consider reaction mechanism.

Language: Английский

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Reductive amination: Methods for cell-free and whole-cell biocatalysis

Methods in enzymology on CD-ROM/Methods in enzymology, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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Modular Chemoenzymatic Cascade for Highly Diastereo- and Enantioselective Synthesis of 1,3-Disubstituted Tetrahydroisoquinolines

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5426 - 5434

Published: March 18, 2025

Language: Английский

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Continuous-flow chemoenzymatic conversion of racemic alcohols to enantiopure alcohols and amines

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 580, P. 115094 - 115094

Published: April 8, 2025

Language: Английский

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Mutagenesis of a Single Site Inverts the Stereopreference of Imine Reductase

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2192 - 2199

Published: Jan. 23, 2025

Development of a generally applicable means to invert the stereoselectivity an enzymatic reaction is paramount significance. Through protein structure-guided mutagenesis, Met235 was identified as crucial residue influencing imine reductase AtIRED-catalyzed reduction sterically demanding 1-substituted dihydro-β-carbolines (DHβCs), particularly with single mutants M235A/C/G/I/S/T/V displaying simultaneously inverted and improved catalytic activity relative wild-type (WT) enzyme. Using best variant M235A biocatalyst, five tetrahydro-β-carbolines (THβCs) (R)-configuration were afforded in 48–81% isolated yields 89 → 99% ee. Combined our previous synthesis (S)-stereoisomer using WT other variants, we have established stereocomplementary access these THβCs. Based on solved crystal structure complexed NADP+ substrate 1-t-butyl-DHβC, mutation-induced relief undesired steric clashes rationalized main cause observed inversion enhancement. This influence stereopreference exerted by mutation transferred successfully Y-type IREDs and, part, D-type IREDs, representing first demonstration this kind knowledge transfer between reductases. The current study identifies stereocontrol element it offers potentially generic strategy switch fascinating enzymes.

Language: Английский

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Role of Redox Reactions and AI-Driven Approaches in Enhancing Nutrient Availability for Plants

LatIA, Journal Year: 2025, Volume and Issue: 3, P. 86 - 86

Published: Feb. 19, 2025

Empirical studies have shown that environmental variability in the field remains uncontrolled certain cases, with research often conducted at a limited number of agricultural sites. Direct measurements redox potential soils been reported, yet quantifying rapid changes this variable across microsites proves inaccessible situ. Existing also fail to account for identity reduced or oxidized compounds. Additionally, methodological constraints and researcher bias, particularly focusing on processes sediments, may impair interpretations anabolic reactions resulting from oxidation.Case further indicate effects nitrification, net mineralization, immobilization other nutrients remain unmeasured. As result, increased denitrification might stimulate reducing nitrogen due increasing carbon storage environments where reduction predominates.Given absence specifically exploring balance between oxidation relation nutrient availability, assessing magnitude likelihood shortcomings based prior challenging. serves as foundation understanding how significantly influence dynamics availability larger scales. Future manipulating should consider factors could disproportionately facilitate reductions before an eastward shift occurs response organic matter addition. Addressing these gaps will enhance their role stimulating sulfide responses.

Language: Английский

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Asymmetric Synthesis of N-Hydroxyethyl Amino Indane Derivatives Catalyzed by an Engineered Imine Reductase

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Asymmetric synthesis of chiral N-hydroxyethyl amino indane derivatives remains challenging. In this study, an imine reductase mutant (IR262-F185E/F229L) was identified with high enantioselectivity toward various imino derivatives. Furthermore, a continuous fed-batch strategy designed to avoid the hydrolysis imines, and up 200 mM 1-((2-hydroxyethyl)imino)-2,3-dihydro-1H-indene-4-carbonitrile could be completely converted into (S)-1-((2-hydroxyethyl)amino)-2,3-dihydro-1H-indene-4-carbonitrile in 70% isolated yield >99% ee, demonstrating great potential for ozanimod intermediate industrial applications.

Language: Английский

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Reductive N-Heterocyclic Carbene Catalysis via Hydride Transfer: Generating Homoenolates from Unsaturated Esters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 27, 2025

In N-heterocyclic carbene (NHC) catalysis, the reduction of NHC-bound acyl azolium species is achieved with progress limited to generation ketyl radical intermediates. Here, we report a novel NHC-catalyzed reductive mode for intermediates, which accept hydride generate Breslow intermediate. Then, reaction intermediate chalcone results in formation cyclopentene, demonstrating classic umpolung transformation. We expect that this catalytic will open new avenues synthetic transformations.

Language: Английский

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Expanding the repertoire of imine reductases by mining divergent biosynthetic pathways for promiscuous reactivity

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(12), P. 101160 - 101160

Published: Oct. 24, 2024

Language: Английский

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