Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

Gillespie, James E.; Lam, Nelson Y. S.; Phipps, Robert J.

doi:10.1039/d3sc03293k

Chem. Sci.

2023

DOI: 10.1039/d3sc03293k

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Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

James E. Gillespie,

Nelson Y. S. Lam,

Robert J. Phipps

Abstract: Direct amination of arene C–H bonds is an attractive disconnection to form aniline-derived building blocks. This transformation presents significant practical challenges; classical methods for ortho-selective amination require strongly acidic or...

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Cited by 6 publications

(1 citation statement)

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“…Non-covalent interactions play a vital role in achieving unique regio- and stereoselectivity in enzyme catalysis, indicating enormous potential for organic chemists to conceive new strategies of harnessing such interactions . In a recent study, Phipps and colleagues showcased an ortho -selective C–H amination facilitated by non-covalent interactions between an anionic substrate and an ammonium radical (Figure B) . Nevertheless, the meta -C–H amination through a non-covalent directing strategy remains unknown to date.…”

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confidence: 99%

Advancing Meta-Selective C–H Amination through Non-Covalent Interactions

Lv,

Hu,

Zhang

et al. 2023

J. Am. Chem. Soc.

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Regioselective C−H amination of simple arenes is highly desirable, but accessing meta-sites of ubiquitous arenes has proven challenging due to the lack of both electronic and spatial preference. This study demonstrates the successful use of various privileged nitrogen-containing functionalities found in pharmaceutical compounds to direct meta-C−H amination of arenes, overcoming the long-standing requirement for a redundant directing group. The remarkable advancements in functional group accommodation for precise regiochemical control were achieved through the discovery of an unprecedented organo-initiator and the strategic utilization of non-covalent interactions. This protocol has been successfully applied in the concise synthesis and late-stage derivatization of drug molecules, which would have been otherwise challenging to achieve.

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mentioning

confidence: 99%

Advancing Meta-Selective C–H Amination through Non-Covalent Interactions

Lv,

Hu,

Zhang

et al. 2023

J. Am. Chem. Soc.

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Homogeneous Iron Catalyzed C−H Amination

Possenti,

Olivo

2024

ChemCatChem

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Iron‐catalyzed C—H amination is emerging as an attractive and sustainable method to install amine functionalities into organic compounds. Amination of C(sp3)—H bonds is usually mediated by an iron‐nitrene intermediate via a Hydrogen Atom Abstraction/Radical Recombination mechanism reminiscent of biomimetic C—H oxidation. Accordingly, this transformation can be catalyzed by engineered iron enzymes, heme and nonheme iron complexes as well as iron salts, although it is often limited to intramolecular reactions and/or activated positions. Aromatic C(sp2)—H amination is mediated by addition of electrophilic iron nitrenes or protonated N‐radical intermediates (produced with Fe catalysts) to aromatic systems. Again, high selectivity is obtained via (pseudo) intramolecular reactions. From a mechanistic perspective, several iron nitrene intermediates have been isolated and characterized over the years in different ligand scaffolds and iron oxidation states. Structure‐activity correlations have been drawn only in few cases and point to a key role of the spin density on the nitrene ligand and of the iron oxidation state. This review describes the state of the art for homogeneous iron catalyzed C(sp3)—H and C(sp2)—H amination focusing on the last 5 years (2019‐2023) from a mechanism‐driven catalyst design perspective.

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Hydroxylamine‐O‐Sulfonic Acid (HOSA): A Recent Synthetic Overview

Kumar,

Divedi,

Chandra

et al. 2024

ChemistrySelect

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Hydroxylamine‐O‐sulfonic acid has been used as a versatile nitrogen source in synthetic organic chemistry. It has dual function and utilized both as a nucleophile and an electrophile during different synthetic transformations. This reagent is stable and easy to handle in both aqueous and organic solvents. It can be used with different functional groups under mild reaction conditions, making its widely applicable for constructing complex molecules. It has been utilized for various applications such as agrochemicals, pharmaceuticals, and polymer industries in the formation of S−N, C−N, O−N, and N−N bonds, as well as for efficient cyclization reactions under metal‐free conditions with excellent stereo– and regioselectivity. The present review provides a brief overview of all the advancements made in the past two decades using hydroxylamine‐O‐sulfonic acid as a nitrogen source.

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Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

Abstract: Direct amination of arene C–H bonds is an attractive disconnection to form aniline-derived building blocks. This transformation presents significant practical challenges; classical methods for ortho-selective amination require strongly acidic or...

Cited by 6 publications

References 73 publications

Advancing Meta-Selective C–H Amination through Non-Covalent Interactions

Advancing Meta-Selective C–H Amination through Non-Covalent Interactions

Homogeneous Iron Catalyzed C−H Amination

Hydroxylamine‐O‐Sulfonic Acid (HOSA): A Recent Synthetic Overview

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