Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry DOI
Vladimir A. Larionov,

Nadezhda V. Stoletova,

Victor I. Maleev

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(20), P. 4325 - 4367

Published: Sept. 2, 2020

Abstract Chiral amino acids (AAs), being the main “building” blocks of living organisms, are also an important class organic compounds which broadly applied in synthetic chemistry, biochemistry, catalysis and designing new drugs. According to industrial‐commodity market, chiral non‐proteinogenic AAs containing various functional groups come fore. To date, radical cross‐coupling reactions becoming option as attractive powerful tool for AA syntheses. Owing mild reaction conditions high functional‐group tolerance, chemistry represents ideal strategy synthesis challenging complex AAs. Moreover, allows introducing residue into drug scaffolds natural compounds. In present review, we wish summarize discuss all reported date methods asymmetric using by presenting a comprehensive account literature this field going back 1990. We especially emphasize on approach and, exclusively, stereoselective α‐, β‐, γ‐AAs derivatives employing different type initiators starting from AIBN organostannes ending with photoredox catalysis. Furthermore, mechanism will be discussed. magnified image

Language: Английский

Reductive Coupling of Nitroarenes and HCHO for General Synthesis of Functional Ethane-1,2-diamines by a Cobalt Single-Atom Catalyst DOI
Jialu Sun, Huanfeng Jiang, Pierre H. Dixneuf

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17329 - 17336

Published: July 7, 2023

Despite the extensive applications, selective and diverse access to N,N'-diarylethane-1,2-diamines remains, date, a challenge. Here, by developing bifunctional cobalt single-atom catalyst (CoSA-N/NC), we present general method for direct synthesis of such compounds via reductive coupling cheap abundant nitroarenes formaldehyde, featuring good substrate functionality compatibility, an easily accessible base metal with excellent reusability, high step atom efficiency. Mechanistic studies reveal that N-anchored single atoms (CoN4) serve as catalytically active sites reduction processes, N-doped carbon support enriches HCHO timely trap in situ formed hydroxyamines affords requisite nitrones under weak alkaline conditions, subsequent inverse electron demand 1,3-dipolar cycloaddition imines followed hydrodeoxygenation cycloadducts furnishes products. In this work, concept catalyst-controlled nitroarene create specific building blocks is anticipated develop more useful chemical transformations.

Language: Английский

Citations

37
Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane DOI
Yao Xu, Haixiang Gao,

Chengkai Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 13, 2023

Abstract By resorting to the principle of remote activation, we herein demonstrate first photoredox catalyzed (3+3) dipolar cycloaddition nitrones with aryl cyclopropanes. Key fidelity reaction resides in a facile manner substrate activation by single‐electron transfer (SET) oxidation catalysis, and takes place through stepwise cascade encompassing three‐electron‐type nucleophilic substitution triggered cyclopropane ring‐opening diastereoselective 6‐endo‐ trig radical cyclization manifold. The proceeds under mild conditions excellent regio‐ stereoselectivity, nicely complementing well‐developed Lewis acid donor‐acceptor Other merits protocol include wide scope cyclopropanes diversified patterns good functional‐group compatibility. A mechanism involving an cation promoted mode was also proposed supported mechanistic experiments.

Language: Английский

Citations

25
Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones DOI

Liren Xu,

Tilong Yang, Hao Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 17, 2024

Abstract Owing to their distinctive 1,3‐dipolar structure, the catalytic asymmetric hydrogenation of nitrones hydroxylamines has been a formidable and longstanding challenge, characterized by intricate enantiocontrol susceptibility N−O bond cleavage. In this study, transfer were accomplished with tethered TsDPEN‐derived cyclopentadienyl rhodium(III) catalyst (TsDPEN: p ‐toluenesulfonyl‐1,2‐diphenylethylene‐1,2‐diamine), reaction proceeds via novel 7‐membered cyclic transition state, producing chiral up 99 % yield >99 ee. The practical viability methodology was underscored gram‐scale reactions subsequent transformations. Furthermore, mechanistic investigations DFT calculations also conducted elucidate origin enantioselectivity.

Language: Английский

Citations

9
Multicomponent Reductive Coupling for Selective Access to Functional γ-Lactams by a Single-Atom Cobalt Catalyst DOI
Jialu Sun, Huanfeng Jiang, Pierre H. Dixneuf

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: March 21, 2024

Despite their significant importance to numerous fields, the difficulties in direct and diverse synthesis of α-hydroxy-γ-lactams pose substantial obstacles practical applications. Here, we designed a nitrogen TiO2 co-doped graphitic carbon-supported material with atomically dispersed cobalt sites (CoSA-N/NC-TiO2), which was successfully applied as multifunctional catalyst establish general method for construction from cheap abundant nitro(hetero)arenes, aldehydes, H2O alkynoates. The striking features operational simplicity, broad substrate functionality compatibility (>100 examples), high step atom efficiency, good selectivity, exceptional reusability highlight practicality this new catalytic transformation. Mechanistic studies reveal that active CoN4 species dopants exhibit synergistic effect on formation key acid-masked nitrones; subsequent nucleophilic addition alkynoates followed by successive reduction, alkenyl hydration, intramolecular ester ammonolysis delivers desired products. In work, concept reduction interruption leading reaction route will open door further develop useful transformations rational design.

Language: Английский

Citations

9
Synthesis of Benzazepines Bearing Three Contiguous Carbon Stereocenters through Pd(II)-Catalyzed [3 + 2] Cycloaddition of N-Aryl Nitrones with Allenoates DOI

S.W. Xin,

Shan Chen, Jason Z. Qin

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

A cascade reaction of Pd(II)/dppben-catalyzed [3 + 2] cycloaddition N-aryl nitrones with allenoates and sequential reduction has been developed for the synthesis functionalized benzazepines bearing three contiguous carbon stereocenters in moderate to good yields ranging from 15 82% high diastereoselectivity. The obtained could be converted into various benzazepine scaffolds, an estrone-derived scaffold was prepared over four steps estrone. More importantly, chiral 88% ee value auxiliary.

Language: Английский

Citations

1
Reduction-Interrupted Tandem Reaction for General Synthesis of Functional Amino Acids by a Heterogeneous Cobalt Catalyst DOI

Hui‐Liang Hua,

Chenggang Ci, Pierre H. Dixneuf

et al.

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

Published: Feb. 11, 2025

Despite their significant importance in numerous fields, the challenges direct and diverse synthesis of γ-amino-α-hydroxybutyric acids (AHBAs) pose substantial obstacles to explore functions. Here, by preparation a N-doped carbon-supported bifunctional cobalt catalyst (Co-DAPhen/C), it was applied develop reductive tandem reaction for general AHBA derivatives from cheap abundant nitroarenes, formaldehyde, acrylates. This catalytic three-component features broad substrate functionality tolerance, an easily accessible reusable catalyst, high step atom economy. The active Co sites are involved mild reduction processes with formic acid, whereas carbon support enriches HCHO acrylates physical adsorption, thus favoring capture hydroxylamine nitrone intermediates via condensation 1,3-dipolar cycloaddition, respectively. Such metal–support synergy interrupts conventional nitroarenes into anilines results novel route. In this work, concept merging effective intermediate transformations is anticipated more useful reactions rational design.

Language: Английский

Citations

1
Spiro‐2‐oxindoles via 1,3‐dipolar cycloadditions. A decade update DOI
Giorgio Molteni, Alessandra Silvani

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(11), P. 1653 - 1675

Published: Feb. 23, 2021

Abstract The great variety of spirooxindole three‐dimensional scaffolds encompasses relevant bioactive natural alkaloids as well useful therapeutic agents. In view the challenging features skeletons and their desirable properties, several synthetic routes have been devoted to preparation. Because both 1,3‐dipolar species 2‐oxindoles bearing a C=X double bond (X=C<, N−, O) in 3‐position, prominent role relies upon cycloaddition key step whole sequence. present paper aims discuss developments field synthesis via occurred 2011–2020 decade. literature data on this subject are reviewed systematic way according type 1,3‐dipole oxindole dipolarophile.

Language: Английский

Citations

49
Reductive Functionalization of Amides in Synthesis and for Modification of Bioactive Compounds DOI Creative Commons
Paweł J. Czerwiński, Bartłomiej Furman

Frontiers in Chemistry, Journal Year: 2021, Volume and Issue: 9

Published: April 26, 2021

In this review, applications of the amide reductive functionalization methodology for synthesis and modification bioactive compounds are covered. A brief summary different protocols is presented in introduction, followed by synthetic application these late-stage functionalization, leading to known pharmaceuticals or their derivatives, including bioisosteres, with potential higher activity as main axis article. The approach natural products based on reduction also discussed; however, given a condensed form focusing recent yet unexplored due number recently published excellent reviews covering topic. aim review illustrate amides an elegant useful tool inspire further work field.

Language: Английский

Citations

46
Enantioselective Synthesis of Cyclic Nitrones by Chemoselective Intramolecular Allylic Alkylation of Oximes DOI
Tobias Sandmeier, Erick M. Carreira

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(18), P. 9913 - 9918

Published: Feb. 8, 2021

Abstract The enantio‐ and chemoselective iridium‐catalyzed N‐allylation of oximes is described for the first time. Intramolecular kinetic resolution provides access to cyclic nitrones enantioenriched aliphatic allylic alcohols. Salient features this transformation are its ability employ E/Z‐isomeric mixtures oxime starting materials convergently high functional group tolerance. implementation N‐allylation/1,3‐dipolar cycloaddition reaction sequences furnishes tricyclic isoxazolidines in highly diastereoselective fashion. synthetic utility approach demonstrated by efficient, formal synthesis marine natural product (+)‐halichlorine.

Language: Английский

Citations

42
A Porous Crystalline Nitrone‐Linked Covalent Organic Framework** DOI
Daria Kurandina, Banruo Huang, Wentao Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 13, 2023

Herein, we report the synthesis of a nitrone-linked covalent organic framework, COF-115, by combining N, N', N'''-(ethene-1, 1, 2, 2-tetrayltetrakis(benzene-4, 1-diyl))tetrakis(hydroxylamine) and terephthaladehyde via polycondensation reaction. The formation nitrone functionality was confirmed solid-state 13 C multi cross-polarization magic angle spinning NMR spectroscopy C-isotope-labeled COF-115 Fourier-transform infrared spectroscopy. permanent porosity evaluated through low-pressure N2 , CO2 H2 sorption experiments. Water vapor carbon dioxide analysis isoreticular imine-linked COF indicated superior potential N-oxide-based porous materials for atmospheric water harvesting capture applications. Density functional theory calculations provided valuable insights into difference between adsorption properties these COFs. Lastly, photoinduced rearrangement to associated amide-linked material successfully demonstrated.

Language: Английский

Citations

18