Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis** DOI Creative Commons
Weigang Zhang, Tao Liu, Hwee Ting Ang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(44)

Published: Sept. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Language: Английский

Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides DOI
Xiaoyan Jia,

Gui-Lin Hao,

Mengxia Feng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9768 - 9778

Published: March 28, 2024

A rhodium-catalyzed 3-component conjunctive diastereo- and regioselective arylamidation of (homo)allylic sulfides, organon boronic acids, dioxazolones is reported. These reactions deliver the 1,2-insertion 2,1-insertion products, respectively, for allylic sulfides homoallylic sulfides. The enantioselective terminal internal achieved, furnishing various 1,3-N,S compounds featuring one or two contiguous stereocenters in high yields with enantioselectivities. Mechanistic studies suggest a change turnover-limiting selectivity-determining steps induced by native easily removable sulfide group.

Language: Английский

Citations

2
Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines DOI Creative Commons
Étienne Derat, Géraldine Masson, Aurélie Claraz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 30, 2024

An electrochemical radical Truce Smiles rearrangement of N-allylbenzamides is documented herein. The selective 1,4-aryl migration was triggered by the fluoromethylation alkene providing a direct route to fluoro derivatives highly privileged β-arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current drive oxidative process under mild reaction conditions. It accommodates variety migratory aryl groups with different electronic properties substitution patterns. Careful selection protecting group on nitrogen atom N-allylbenzamide crucial outcompete undesired 6-endo cyclization achieve high level selectivity towards migration. DFT calculations support mechanism unveil origin between two competitive pathways.

Language: Английский

Citations

2
A Povarov-Type Reaction to Access Tetrahydroquinolines from N-Benzylhydroxylamines and Alkenes in HFIP DOI Creative Commons
Valentyn Pozhydaiev,

Daniella Al-Othman,

Joseph Moran

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(76), P. 10504 - 10507

Published: Jan. 1, 2024

Here, we report the synthesis of tetrahydroquinolines between newly developed

Language: Английский

Citations

2
Oxydiazomethylation of Alkenes via Photoredox Catalysis DOI

Ying Zeng,

Xiaochan Zheng,

Lixing Shen

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

α-Diazoesters belong to significantly important carbenoid precursors in synthetic chemistry. Diazomethylation-based difunctionalization of alkenes is highly valuable but remain nontrivial. Herein, we reported a general and modular approach for the direct 1,2-oxydiazomethylation through visible-light photoredox catalysis. This process exploits photocatalyzed strategy convert γ-formyloxyl-α-diazoesters using α-diazo iodonium salts as carbyne precursors, featuring wide substrate tolerance broad late-stage diversifications. Mechanistic studies suggest that formation γ-carbocation-tethered α-diazoesters plays crucial role trapping DMF H

Language: Английский

Citations

2
A Scalable and Metal-Free Synthesis of Indazoles from 2-Aminophenones and In Situ Generated De-Boc-Protected O-Mesitylsulfonyl Hydroxylamine Derivatives DOI
Jinlong Wang, Dongmin Shi, Zihao Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(18), P. 13049 - 13056

Published: Aug. 30, 2023

A one-pot metal-free protocol to access indazoles from easily available 2-aminophenones and hydroxylamine derivatives has been achieved. The reaction is operationally simple, mild, insensitive air moisture. broad range of were prepared in good excellent yield (up 97% yield), the displayed a functional group tolerance. was performed at gram scale, its synthetic application exhibited through rapid efficient preparation bioactive molecule YC-3 FDA-approved drug axitinib.

Language: Английский

Citations

5
Recent Advances in Nonprecious Metal Catalysis DOI
David J. Bernhardson, Eric C. Hansen, Aran K. Hubbell

et al.

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(11), P. 1913 - 1930

Published: Sept. 13, 2023

As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight advancements. We seek raise awareness both current art and need continue development toward broader application or earth-abundant metals chemical pharmaceutical industries.

Language: Английский

Citations

5
I2-Mediated [6 + 1] Annulation of Alkynes with MsONH3OTf: Direct Synthesis of Benzo[b]azepines DOI

Daijiao Zhuang,

Shixuan Jiang,

Youzhi Wang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(17), P. 3007 - 3012

Published: April 21, 2023

The synthesis of benzo[b]azepines using protonated aminating reagent (MsONH3OTf) and alkynes through I2-mediated [6 + 1] annulation reaction has been developed. This protocol features excellent functional group tolerance mild conditions affords the in moderate to good yields under metal-free conditions.

Language: Английский

Citations

4
Iron(II)‐Catalyzed 1,2‐Diamination of Styrenes Installing a Terminal NH2 Group Alongside Unprotected Amines DOI Creative Commons
Valentyn Pozhydaiev,

Antonio Paparesta,

Joseph Moran

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 17, 2024

1,2-Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N-functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2-diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N-heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2-aminothiolation styrenes.

Language: Английский

Citations

1
Synthesis of 1-Aryltetralins via Re2O7/HReO4 Mediated Intramolecular Hydroarylations DOI

Rukhsar Gul,

Liqun Hu,

Yibing Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(16), P. 12079 - 12086

Published: Aug. 10, 2023

Here, we describe highly efficient intramolecular hydroarylations mediated by Re2O7/HReO4. Styrene derivatives of different electronic properties have been activated to effect a challenging hydroarylation for the facile access various substituted 1-aryltetralin structures. This method is characterized mild reaction conditions, broad substrate scope, high chemical yields, and 100% atom economy. The potential synthetic application this methodology was exemplified total synthesis an isoCA-4 analogue.

Language: Английский

Citations

2
Iron-Mediated Dialkylation of Alkenylarenes with Benzyl Bromides DOI

Daniel M. Lux,

Daniel J. Lee, Rishi R. Sapkota

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: April 4, 2024

We disclose a method for the dibenzylation of alkenylarenes with benzyl bromides using iron powder. This reaction generates branched alkyl scaffolds adorned functionalized aryl rings through formation two new C(sp3)–C(sp3) bonds at vicinal carbons alkenes. protocol tolerates electron-rich, electron-neutral, and electron-poor alkenylarenes. Mechanistic studies suggest benzylic radical intermediates as result single-electron transfer from iron, which is intercepted by

Language: Английский

Citations

0