Expeditious Synthesis of Highly Functional 4-Trifluoromethyl-Substituted Oxazoles Enabled by Cobalt(II) Metalloradical Catalysis DOI

Hang Wang,

Qingyun Duan, Baiquan Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(2), P. 759 - 767

Published: Dec. 25, 2024

A synthetic strategy for the catalytic cycloaddition of α-trifluoromethyl-α-diazoketones with nitriles has been achieved based on cobalt(II) metalloradical catalysis. The easily accessible starting materials, cost-effective catalyst, and experimental simplicity rendered this protocol a robust practical approach to construct diverse functionalized 4-CF3-substituted oxazoles high efficiency. wide substrate scope both α-trifluoromethylated diazoketones is amenable system. level functional group tolerance provides several opportunities precise late-stage modifications bioactive drug-like molecules. Mechanistic experiments spectroscopic investigations confirm radical nature reaction reveal involvement monocarbene biscarbene intermediates during process.

Language: Английский

Iron(III)-based metalloradical catalysis for asymmetric cyclopropanation via a stepwise radical mechanism DOI
Wan‐Chen Cindy Lee, Duo‐Sheng Wang, Yiling Zhu

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(11), P. 1569 - 1580

Published: Sept. 7, 2023

Language: Английский

Citations

57
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, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 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.

Language: Английский

Citations

28
Asymmetric Radical Bicyclization for Stereoselective Construction of Tricyclic Chromanones and Chromanes with Fused Cyclopropanes DOI
Wan‐Chen Cindy Lee, Jingyi Wang, Yiling Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11622 - 11632

Published: May 2, 2023

Asymmetric radical bicyclization processes have been developed via metalloradical catalysis (MRC) to stereoselectively construct chiral chromanones and chromanes bearing fused cyclopropanes. Through optimization of a versatile

Language: Английский

Citations

23
Vitamin B12‐Photocatalyzed Cyclopropanation of Electron‐Deficient Alkenes Using Dichloromethane as the Methylene Source** DOI
John Hayford G. Teye‐Kau, Mayokun J. Ayodele, Spencer P. Pitre

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 28, 2023

Abstract The cyclopropyl group is of great importance in medicinal chemistry, as it can be leveraged to influence a range pharmaceutical properties drug molecules. This report describes Vitamin B 12 ‐photocatalyzed approach for the cyclopropanation electron‐deficient alkenes using dichloromethane (CH 2 Cl ) methylene source. reaction proceeds good excellent yields under mild conditions, has functional compatibility, and highly chemoselective. scope could also extended preparation D ‐cyclopropyl methyl‐substituted adducts starting from CD 1,1‐dichloroethane, respectively.

Language: Английский

Citations

23
Asymmetric Three-Component Radical Alkene Carboazidation by Direct Activation of Aliphatic C–H Bonds DOI
Liang Ge,

Hongkai Wang,

Yangbin Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13347 - 13355

Published: May 6, 2024

Azide compounds are widely present in natural products and drug molecules, their easy-to-transform characteristics make them used the field of organic synthesis. The merging transition-metal catalysis with radical chemistry offers a versatile platform for carboazidation alkenes, allowing rapid assembly highly functionalized azides. However, direct use readily available hydrocarbon feedstocks as sp

Language: Английский

Citations

16
Stereoselective gem-Difunctionalization of Diazo Compounds with Vinyl Sulfoxonium Ylides and Thiols via Metalloradical Catalysis DOI

Srashti Bhardwaj,

Dinesh Kumar Gopalakrishnan,

Shalu Deshwal

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2805 - 2815

Published: Feb. 8, 2024

Multicomponent reactions that involve carbenes with nucleophiles and electrophiles have demonstrated broad applications in synthetic chemistry. However, because of the high reactivity transient carbenes, involving two carbene precursors nucleophile presence a metal catalyst remain unexplored. Herein, three-component stereoselective gem-difunctionalization diazo compounds thiols vinyl sulfoxonium ylide is disclosed via Co(II)-based metalloradical catalysis. The key aspect present strategy to exploit intrinsic difference ylides thiol catalysts. Doyle–Kirmse rearrangement sulfonium involves convergent assembly situ-generated intermediates, such as allyl sulfide α- metalloalkyl radical complex, provide expeditious access tertiary scaffolds. Combined experimental quantum chemical calculations unveil intricate mechanism this reaction. Furthermore, theoretical studies on noncovalent interactions selectivity-determining transition states explain origin experimentally obtained diastereoselectivity.

Language: Английский

Citations

6
Catalytic Olefin Cyclopropanation with In Situ-Generated Dialkyl Diazomethanes via Co(II)-Based Metalloradical Catalysis DOI
Bao‐Gui Cai, Claire Empel, Sripati Jana

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11851 - 11856

Published: Aug. 23, 2023

The synthesis of dialkyl-substituted cyclopropanes is an important challenge in with applications drug discovery and agrochemistry. Herein, we report on the gem-dialkyl situ-generated dialkyl diazo compounds under Bamford–Stevens conditions. A simple cobalt catalyst was identified to be optimal achieve high yields. Experimental computational studies suggest participation a metalloradical reaction mechanism that facilitates carbene transfer reactions provides access single step.

Language: Английский

Citations

15
New mode of asymmetric induction for enantioselective radical N-heterobicyclization via kinetically stable chiral radical center DOI Creative Commons
Hao Xu, Duo‐Sheng Wang, Zhenyu Zhu

et al.

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 283 - 298

Published: Oct. 11, 2023

Language: Английский

Citations

15
Highly diastereoselective and enantioselective cyclopropanation of alkenes catalyzed by a chiral iridium(III) porphyrin complex DOI
Shengyu Li,

Shanshan Yuan,

Xiao-Ming Zhao

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101262 - 101262

Published: Feb. 1, 2025

Language: Английский

Citations

0
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

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

Citations

0