Fe‐Catalyzed α‐C(sp3)–H Amination of N‐Heterocycles DOI Creative Commons
Andrea Geraci, Olivier Baudoin

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Окт. 16, 2024

Abstract Nitrogen‐heterocycles are privileged structures in both marketed drugs and natural products. On the other hand, C−H amination reactions furnish unconventional straightforward approaches for construction of C−N bonds. Yet, most known methods rely on precious metal catalysts. Herein we report a site‐selective intermolecular C(sp 3 )−H N‐heterocycles, catalyzed by inexpensive FeCl 2, which allows functionalization wide range pharmaceutically relevant cyclic amines. The occurs site‐selectively α‐position to nitrogen atom, even when weaker bonds present, furnishes Troc‐protected aminals or amidines. method employs N‐heterocycle as limiting reagent is applicable late‐stage complex molecules. Its synthetic potential was further illustrated through derivatization α‐aminated products application concise total synthesis reported structure senobtusin. Mechanistic studies allowed propose plausible reaction mechanism involving turnover‐limiting Fe‐nitrene generation followed fast H atom transfer radical rebound.

Язык: Английский

Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions DOI Creative Commons
Wan‐Chen Cindy Lee, X. Peter Zhang

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 13, 2024

Abstract Since Friedrich Wöhler's groundbreaking synthesis of urea in 1828, organic over the past two centuries has predominantly relied on exploration and utilization chemical reactions rooted two‐electron heterolytic ionic chemistry. While one‐electron homolytic radical chemistry is both rich fundamental reactivities attractive with practical advantages, synthetic application been long hampered by formidable challenges associated control reactivity selectivity high‐energy intermediates. To fully harness untapped potential for synthesis, there a pressing need to formulate radically different concepts broadly applicable strategies address these outstanding issues. In pursuit this objective, researchers have actively developing metalloradical catalysis (MRC) as comprehensive framework guide design general approaches controlling stereoselectivity reactions. Essentially, MRC exploits metal‐centered radicals present open‐shell metal complexes catalysts activation substrates generate metal‐entangled key intermediates govern reaction pathway stereochemical course subsequent catalytic processes. Different from conventional transition complexes, operates through utilizing stepwise mechanisms.

Язык: Английский

Процитировано

27
Direct synthesis of branched amines enabled by dual-catalyzed allylic C─H amination of alkenes with amines DOI Creative Commons
Yufeng Ren, Bi-Hong Chen, Xiaoyi Chen

и другие.

Science Advances, Год журнала: 2024, Номер 10(14)

Опубликована: Апрель 5, 2024

Direct conversion of hydrocarbons into amines represents an important and atom-economic goal in chemistry for decades. However, intermolecular cross-coupling terminal alkenes with to form branched remains extremely challenging. Here, a visible-light Co-dual catalyzed direct allylic C─H amination free afford has been developed. Notably, challenging aliphatic strong coordinating effect can be directly used as C─N coupling partner couple bond advanced molecular complexity. Moreover, the reaction proceeds exclusive regio- chemoselectivity at more steric hinder position deliver primary, secondary, tertiary diverse substitution patterns that are difficult access otherwise.

Язык: Английский

Процитировано

7
Stereospecific Enzymatic Conversion of Boronic Acids to Amines DOI

Deirdre Hanley,

Zi‐Qi Li,

Shilong Gao

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19160 - 19167

Опубликована: Июль 3, 2024

Boronic acids and esters are highly regarded for their safety, unique reactivity, versatility in synthesizing a wide range of small molecules, bioconjugates, materials. They not exploited biocatalytic synthesis, however, because enzymes that can make, break, or modify carbon–boron bonds rare. We wish to combine the advantages boronic molecular assembly with biocatalysis, which offers potential unsurpassed selectivity efficiency. Here, we introduce an engineered protoglobin nitrene transferase catalyzes new-to-nature amination using hydroxylamine. Initially targeting aryl acids, show enzyme produce array anilines high yields total turnover numbers (up 99% yield >4000 TTN), water boric acid as only byproducts. also demonstrate is effective bench-stable esters, hydrolyze situ corresponding acids. Exploring enzyme's capacity enantioselective catalysis, found racemic alkyl ester affords enantioenriched amine, transformation achieved chemocatalysts. The formation exclusively unrearranged product during radical clock reaction's stereospecificity support two-electron process akin 1,2-metallate shift mechanism. developed enables new routes chiral amines.

Язык: Английский

Процитировано

7
Iron-catalysed nitrene transfer reaction to form C N bonds DOI

Hillol Khatua,

Subrata Das,

Sima Patra

и другие.

Tetrahedron Letters, Год журнала: 2024, Номер 144, С. 155136 - 155136

Опубликована: Июнь 12, 2024

Язык: Английский

Процитировано

6
Visible-Light-Promoted Enantioselective α-Amidation of Aldehydes by Harnessing Organo-Iron Dual Catalysis DOI
Soumyadip Hore, Jiwoo Jeong, Dongwook Kim

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22172 - 22179

Опубликована: Июль 30, 2024

The strategic integration of organocatalysis with transition-metal catalysis to achieve otherwise unattainable stereoselective transformations may serve as a powerful synthetic tool. Herein, we present synthetically versatile α-amidation aldehydes by leveraging dual iron and chiral enamine in an enantioselective manner (up >99:1 er). Experimental computational studies have led us propose new mechanistic platform, wherein visible-light-promoted LMCT generates [Fe(II)Cl

Язык: Английский

Процитировано

6
Catalytic Metalloradical System for Radical 1,6-C(sp3)–H Amination with Concurrent Control of Site-, Chemo-, and Enantio-selectivity DOI
Yiling Zhu, Wan‐Chen Cindy Lee, X. Peter Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

A catalytic radical process has been developed via metalloradical catalysis (MRC) for 1,6-C(sp3)-H amination with concurrent control of site-, chemo-, and enantioselectivity. Supported by an optimal D2-symmetric chiral amidoporphyrin ligand, the Co(II)-based system effectively catalyzes chemoselective propargylic, allylic, benzylic C-H bonds at 1,6- over 1,5-positions alkoxysulfonyl azides, achieving high This Co(II)-catalyzed process, which operates room temperature, is applicable to a broad range azides tolerance functional groups, enabling efficient construction six-membered sulfamidates in yields excellent enantioselectivities. Comprehensive experimental investigations, complemented computational studies, elucidate stepwise mechanism underlying this transformation. The resulting cyclic from enantioselective can undergo stereospecific ring-opening reactions various nucleophiles, affording γ-functionalized α-chiral amines while retaining original enantiopurity. Since are readily synthesized widely available alcohols through nucleophilic azide transfer, union ionic processes constitutes versatile 1,3-difunctionalization alcohols.

Язык: Английский

Процитировано

0
Visible-Light-Driven Iron-Catalyzed Intermolecular Benzylic C(sp3)–H Amination with 1,2,3,4-Tetrazoles DOI
Yan Du, Jingjing Tang,

Yarong Wang

и другие.

Organic Letters, Год журнала: 2024, Номер 26(3), С. 664 - 669

Опубликована: Янв. 16, 2024

A visible-light-driven iron-catalyzed C(sp3)–H amination of diphenylmethane derivatives with 1,2,3,4-tetrazoles under mild conditions has been developed. The reaction proceeds photosensitizer-free and features satisfactory to good yields. Mechanistic studies revealed that the proceeded via an iron–nitrene intermediate, H atom abstraction was rate-determining step. Computational showed denitrogenation 1,2,3,4-tetrazole depends on conversion sextet ground state 1,2,3,4-tetrazole-bounding iron species quartet spin visible-light irradiation.

Язык: Английский

Процитировано

3
Stereogenic-at-iron mesoionic carbene complex for enantioselective C–H amidation DOI Creative Commons

Nemrud Demirel,

Mahiob Dawor,

Greta Nadler

и другие.

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Stereogenic-at-iron complexes, featuring strongly σ-donating mesoionic carbene (MIC) ligands, exhibit enhanced catalytic efficiency compared to their normal N-heterocyclic congeners in nitrene-mediated ring-closing C(sp 3 )–H amidations.

Язык: Английский

Процитировано

3
Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions DOI Creative Commons
Wan‐Chen Cindy Lee, X. Peter Zhang

Angewandte Chemie, Год журнала: 2024, Номер 136(20)

Опубликована: Март 13, 2024

Abstract Since Friedrich Wöhler's groundbreaking synthesis of urea in 1828, organic over the past two centuries has predominantly relied on exploration and utilization chemical reactions rooted two‐electron heterolytic ionic chemistry. While one‐electron homolytic radical chemistry is both rich fundamental reactivities attractive with practical advantages, synthetic application been long hampered by formidable challenges associated control reactivity selectivity high‐energy intermediates. To fully harness untapped potential for synthesis, there a pressing need to formulate radically different concepts broadly applicable strategies address these outstanding issues. In pursuit this objective, researchers have actively developing metalloradical catalysis (MRC) as comprehensive framework guide design general approaches controlling stereoselectivity reactions. Essentially, MRC exploits metal‐centered radicals present open‐shell metal complexes catalysts activation substrates generate metal‐entangled key intermediates govern reaction pathway stereochemical course subsequent catalytic processes. Different from conventional transition complexes, operates through utilizing stepwise mechanisms.

Язык: Английский

Процитировано

2
Nickel/Photoredox Dual Catalytic Chan‐Lam Coupling of Aryl Azides and Arylboric Acids DOI

Xia Ge,

Haojie Ji,

Hongjian Lu

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2228 - 2234

Опубликована: Май 14, 2024

Comprehensive Summary Unsymmetrical diarylamines are crucial components in many pharmaceuticals and functional materials. In this study, we introduce an efficient Chan‐Lam cross‐coupling method that utilizes phenylboronic acids aryl azides as coupling agents a redox‐neutral environment, enabled by synergistic nickel/photoredox catalytic system. This approach leverages proton‐coupled electron transfer mechanism to bypass the typical nitrene pathway associated with azides, which is prone intramolecular rearrangement, C—H amination, reductive hydrogenation. Notably, our exhibits broad compatibility variety of groups, including those derived from pharmaceuticals, demonstrating its versatile potential organic synthesis drug modification.

Язык: Английский

Процитировано

2