Homogeneous Iron Catalyzed C−H Amination

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: May 6, 2024

Abstract Iron‐catalyzed C−H amination is emerging as an attractive and sustainable method to install amine functionalities into organic compounds. Amination of C( sp 3 )−H bonds usually mediated by iron‐nitrene intermediate via a Hydrogen Atom Abstraction/Radical Recombination mechanism reminiscent biomimetic oxidation. Accordingly, this transformation can be catalyzed engineered iron enzymes, heme nonheme complexes well salts, although it often limited intramolecular reactions and/or activated positions. Aromatic 2 addition electrophilic nitrenes or protonated N‐radical intermediates (produced with Fe catalysts) aromatic systems. Again, high selectivity obtained (pseudo) reactions. From mechanistic perspective, several nitrene have been isolated characterized over the years in different ligand scaffolds oxidation states. Structure‐activity correlations drawn only few cases point key role spin density on state. This review describes state art for homogeneous focusing last 5 (2019–2023) from mechanism‐driven catalyst design perspective.

Language: Английский

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Biocatalytic Synthesis of α-Amino Esters via Nitrene C–H Insertion

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(40), P. 27267 - 27273

Published: Sept. 27, 2024

α-Amino esters are precursors to noncanonical amino acids used in developing small-molecule therapeutics, biologics, and tools chemical biology. α-C-H amination of abundant inexpensive carboxylic acid through nitrene transfer presents a direct approach α-amino esters. Methods for nitrene-mediated the protic bonds esters, however, underdeveloped. This gap arises because hydrogen atom abstraction (HAA) C-H by electrophilic metal-nitrenoids is slow: preferentially react with polarity-matched, hydridic bonds, even when weaker present. study describes discovery evolution highly stable protoglobin transferases that catalyze enantioselective intermolecular We developed high-throughput assay evaluate activity enantioselectivity mutant enzymes together their sequences using Every Variant Sequencing (evSeq) method. The enabled identification enantiodivergent function at ambient conditions

Language: Английский

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Reaction Discovery Using Spectroscopic Insights from an Enzymatic C–H Amination Intermediate

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20556 - 20562

Published: July 22, 2024

Engineered hemoproteins can selectively incorporate nitrogen from nitrene precursors like hydroxylamine,

Language: Английский

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Mechanistic and Computational Insights into Asymmetric Intramolecular Iron-Catalyzed Nitrene Transfer into Benzylic C–H Bonds

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3789 - 3798

Published: Feb. 18, 2025

Language: Английский

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Chemoenzymatic synthesis

Communications Chemistry, Journal Year: 2025, Volume and Issue: 8(1)

Published: March 13, 2025

Communications Chemistry is pleased to introduce a Collection of research works focused on recent developments within the interdisciplinary field chemoenzymatic synthesis. Here, Guest Editors highlight key themes and look towards future this field.

Language: Английский

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Engineering metalloenzymes for new-to-nature carbene and nitrene transfer biocatalysis

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2025, Volume and Issue: 72, P. 4 - 23

Published: May 1, 2025

Language: Английский

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β-Silicon Effect Enables Metal-Free Site-Selective Intermolecular Allylic C–H Amination

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8865 - 8873

Published: May 23, 2024

α-Amino silanes and their derivatives play pivotal roles across diverse applications, yet current synthetic methods often entail intricate functional group manipulations. Despite the widespread use of allyl as carbon nucleophiles in organic synthesis, participation allylic C–H functionalization has been underexplored. Herein, we unveil a metal-free intermolecular amination facilitated by β-silicon effect. This protocol yields α-amino with exceptional site selectivity. Notably, wide array secondary tertiary are synthesized high without desilylation, owing to mild reaction conditions pathway. Mechanistic elucidations highlight activation effect silyl moiety on alkenes, alongside its stabilizing influence adjacent developing positive charges, which selectively drives closed transition state, ensuring

Language: Английский

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Hot off the press

Natural Product Reports, Journal Year: 2024, Volume and Issue: 41(2), P. 157 - 161

Published: Jan. 1, 2024

A personal selection of 32 recent papers is presented covering various aspects current developments in bioorganic chemistry and novel natural products such as dcalycinumine from Daphniphyllum calycinum .

Language: Английский

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beta-Silicon Effect Enables Metal-Free Site-Selective Intermolecular Allylic C−H Amination

Published: March 8, 2024

α-Amino silanes and their derivatives play pivotal roles across diverse applications, yet current synthetic methods often entail intricate functional group manipulations. Despite the widespread use of allyl as carbon nucleophiles in organic synthesis, participation allylic C–H functionalization has been underexplored. Herein, we unveil a metal-free intermolecular C−H amination facilitated by β-silicon effect. This protocol yields α-amino with exceptional site-selectivity. Notably, wide array secondary tertiary are synthesized high without desilylation, owing to mild reaction conditions unique pathway. Mechanistic elucidations highlight activation effect silyl moiety on alkenes, alongside its stabilizing influence adjacent developing positive charges, which selectively drives closed transition state, ensuring remarkable

Language: Английский

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Progress in Enzyme-Catalyzed C(sp³)–H Amination

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 14139 - 14160

Published: Sept. 11, 2024

Language: Английский

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