Copper-Catalyzed Enantioconvergent Radical C(sp3)–N Cross-Coupling of Activated Racemic Alkyl Halides with (Hetero)aromatic Amines under Ambient Conditions DOI
Ji‐Jun Chen, Jiayong Zhang,

Jia‐Heng Fang

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(27), С. 14686 - 14696

Опубликована: Июль 1, 2023

The enantioconvergent C(sp3)-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N-alkyl yet has remained unexplored due the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed radical activated under ambient conditions. key success is judicious selection appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties formation stable rigid chelating Cu complex. Thus, this kind ligand could not only enhance reducing capability copper provide pathway but also avoid coordination other coordinating heteroatoms, thereby overcoming and/or chiral displacement. This protocol covers wide range coupling partners (89 examples secondary/tertiary bromides/chlorides amines) high functional group compatibility. When allied follow-up transformations, it provides highly flexible platform access synthetically useful amine building blocks.

Язык: Английский

A general copper-catalysed enantioconvergent radical Michaelis–Becker-type C(sp3)–P cross-coupling DOI
Lilei Wang, Huan Zhou, Yuxi Cao

и другие.

Nature Synthesis, Год журнала: 2023, Номер 2(5), С. 430 - 438

Опубликована: Фев. 23, 2023

Язык: Английский

Процитировано

41
Metal-Catalyzed Enantioconvergent Transformations DOI Creative Commons
Miguel Yus, Carmén Nájera, Francisco Foubelo

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(20), С. 11817 - 11893

Опубликована: Окт. 4, 2023

Enantioconvergent catalysis has expanded asymmetric synthesis to new methodologies able convert racemic compounds into a single enantiomer. This review covers recent advances in transition-metal-catalyzed transformations, such as radical-based cross-coupling of alkyl electrophiles with nucleophiles or alkylmetals and reductive two mainly under Ni/bis(oxazoline) catalysis. C–H functionalization can be performed an enantioconvergent manner. Hydroalkylation alkenes, allenes, acetylenes is alternative reactions. Hydrogen autotransfer been applied amination alcohols C–C bond forming reactions (Guerbet reaction). Other metal-catalyzed involve addition allylic systems carbonyl compounds, propargylation phenols, 3-bromooxindoles, allenylation allenolates propargyl bromides, hydroxylation 1,3-dicarbonyl compounds.

Язык: Английский

Процитировано

40
Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers DOI
Liang Fu, Xin Chen, Wenzheng Fan

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(24), С. 13476 - 13483

Опубликована: Июнь 10, 2023

A novel asymmetric radical strategy for the straightforward synthesis of atropisomerically chiral vinyl arenes has been established herein, proceeding through copper-catalyzed atroposelective cyanation/azidation aryl-substituted radicals. Critical to success relay process is capture highly reactive radicals with L*Cu(II) cyanide or azide species. Moreover, these axially vinylarene products can be easily transformed into enriched amides and amines, enantiomerically benzyl nitriles via an axis-to-center chirality transfer process, pure organocatalyst chemo-, diastereo-, enantioselective (4 + 2) cyclization reaction.

Язык: Английский

Процитировано

35
Desymmetrization of Vicinal Bis(boronic) Esters by Enantioselective Suzuki–Miyaura Cross-Coupling Reaction DOI
Mingkai Zhang, Paul S. Lee, Christophe Allais

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8308 - 8313

Опубликована: Апрель 6, 2023

The development of an enantioselective catalytic Suzuki-Miyaura reaction that applies to

Язык: Английский

Процитировано

30
Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds DOI Creative Commons
James L. Douthwaite, Ruheng Zhao, Eunjae Shim

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10930 - 10937

Опубликована: Май 15, 2023

Amines and carboxylic acids are abundant synthetic building blocks that classically united to form an amide bond. To access new pockets of chemical space, we interested in the development amine-acid coupling reactions complement coupling. In particular, formation carbon-carbon bonds by formal deamination decarboxylation would be impactful addition synthesis toolbox. Here, report a cross-coupling alkyl amines aryl C(sp

Язык: Английский

Процитировано

30
Enantioselective Copper-Catalyzed Fukuyama Indole Synthesis from 2-Vinylphenyl Isocyanides DOI Open Access
Till Drennhaus, Dirk Leifert,

Jessika Lammert

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8665 - 8676

Опубликована: Апрель 8, 2023

Enantioenriched chiral indoles are of high interest for the pharmaceutical and agrochemical industries. Herein, we present an asymmetric Fukuyama indole synthesis through a mild efficient radical cascade reaction to access 2-fluoroalkylated 3-(α-cyanobenzylated) by stereochemical control with copper-bisoxazoline complex using 2-vinylphenyl arylisocyanides as acceptors fluoroalkyl iodides C-radical precursors. Radical addition isonitrile moiety, 5-exo-trig cyclization, Cu-catalyzed stereoselective cyanation provide targeted excellent enantioselectivity good yields. Due similar electronic steric properties two aryl substituents be differentiated, enantioselective construction cyano diaryl methane stereocenter is highly challenging. Mechanistic studies reveal negative nonlinear effect which allows proposing model explain outcome. Scalability potential utility enantioenriched hubs tryptamines, indole-3-acetic acid derivatives, triarylmethanes demonstrated, formal natural product analogue disclosed.

Язык: Английский

Процитировано

26
Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(9), С. 6283 - 6293

Опубликована: Фев. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Язык: Английский

Процитировано

18
Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines DOI
Xuan‐Yi Du,

Jia‐Heng Fang,

Ji‐Jun Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9444 - 9454

Опубликована: Март 21, 2024

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, bond formation relies on interaction between nucleophile-sequestered metal complexes and radicals, limiting nucleophile scope to sterically uncongested ones. coupling of congested nucleophiles poses significant challenge due difficulties in transmetalation, restricting reaction generality. Here, we describe probable outer-sphere nucleophilic attack mechanism that circumvents challenging transmetalation associated with nucleophiles. This strategy enables general copper-catalyzed N-alkylation aromatic amines secondary/tertiary alkyl halides exhibits catalyst-controlled stereoselectivity. It accommodates diverse amines, especially bulky secondary primary ones deliver value-added (>110 examples). is expected inspire more nucleophiles, particularly ones, accelerate

Язык: Английский

Процитировано

11
Recent advances in nickel-catalyzed propargylic substitution DOI
Feifei Tong, Dandan Hu, Chun Zhang

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1843 - 1857

Опубликована: Янв. 1, 2024

This work summarizes recent progress in nickel-catalyzed propargylic substitution reactions, categorizing them based on the diverse types of nucleophiles involved, with a specific focus exploring asymmetric transformations.

Язык: Английский

Процитировано

10
Ligand-Enabled Copper(I)-Catalyzed Asymmetric Radical C(sp3)–C Cross-Coupling Reactions DOI
Huan Zhou, Zhong‐Liang Li, Qiang‐Shuai Gu

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(13), С. 7978 - 7986

Опубликована: Июнь 16, 2021

The first-row transition-metal-catalyzed asymmetric C(sp3)–C cross-coupling represents a powerful approach in the expedient synthesis of enantioenriched molecules. Recently, series chiral copper catalysts have been designed to promote variety radical reactions with high efficiency and enantioselectivity. key success is design ligands initiate reaction achieve enantiocontrol over highly reactive prochiral alkyl species. This Perspective will discuss impressive advances provide an outlook on direction further development.

Язык: Английский

Процитировано

54