Enantioselective Hydroxylation of Dihydrosilanes to Si‐Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species DOI
Wu Yang, Lin Liu, Jiandong Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: June 2, 2022

Catalytic enantioselective hydroxylation of prochiral dihydrosilanes with water is expected to be a highly efficient way access Si-chiral silanols, yet has remained unknown up date. Herein, we describe strategy for realizing this reaction: using an alkyl bromide as single-electron transfer (SET) oxidant invoking CuII species and chiral multidentate anionic N,N,P-ligands effective enantiocontrol. The reaction readily provides broad range silanols high enantioselectivity excellent functional group compatibility. In addition, manifest the synthetic potential by establishing two schemes transforming obtained products into compounds structural diversity. Our preliminary mechanistic studies support mechanism involving SET recruiting active catalyst its subsequent σ-metathesis dihydrosilanes.

Language: Английский

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

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(5), P. 430 - 438

Published: Feb. 23, 2023

Language: Английский

Citations

39
Metal-Catalyzed Enantioconvergent Transformations DOI Creative Commons
Miguel Yus, Carmén Nájera, Francisco Foubelo

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(20), P. 11817 - 11893

Published: Oct. 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.

Language: Английский

Citations

38
Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers DOI
Liang Fu, Xin Chen, Wenzheng Fan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(24), P. 13476 - 13483

Published: June 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.

Language: Английский

Citations

32
Desymmetrization of Vicinal Bis(boronic) Esters by Enantioselective Suzuki–Miyaura Cross-Coupling Reaction DOI
Mingkai Zhang, Paul S. Lee, Christophe Allais

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8308 - 8313

Published: April 6, 2023

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

Language: Английский

Citations

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

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10930 - 10937

Published: May 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

Language: Английский

Citations

29
Enantioselective Copper-Catalyzed Fukuyama Indole Synthesis from 2-Vinylphenyl Isocyanides DOI Open Access
Till Drennhaus, Dirk Leifert,

Jessika Lammert

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8665 - 8676

Published: April 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.

Language: Английский

Citations

24
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

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(27), P. 14686 - 14696

Published: July 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.

Language: Английский

Citations

23
Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293

Published: Feb. 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.

Language: Английский

Citations

16
Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines DOI
Xuan‐Yi Du,

Jia‐Heng Fang,

Ji‐Jun Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9444 - 9454

Published: March 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

Language: Английский

Citations

10
Recent advances in nickel-catalyzed propargylic substitution DOI
Feifei Tong, Dandan Hu, Chun Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1843 - 1857

Published: Jan. 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.

Language: Английский

Citations

9