Synthesis of Axially Chiral Vinyl Halides via Cu(I)-Catalyzed Enantioselective Radical 1,2-Halofunctionalization of Terminal Alkynes DOI

Jun-Bin Tang,

Jun-Qian Bian,

Zhihan Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 502 - 513

Published: Dec. 20, 2024

Organohalides are crucial in modern organic synthesis, thanks to their robust and versatile reactivity cross-coupling other key transformations. However, catalytic asymmetric methods for producing enantioenriched organohalides, particularly axially chiral vinyl halides, remain underdeveloped. Here, we present a Cu(I)-catalyzed, highly enantioselective radical alkyne 1,2-halofunctionalization, utilizing custom-designed tridentate anionic N,N,N-ligands with bulky peripheral substituents. This method efficiently employs (hetero)aryl alkyl sulfonyl chlorides, as well α-carbonyl bromides, precursors utilizes diverse range of 2-amino 2-oxy aryl terminal alkynes substrates produce halides. The reaction is scalable gram quantities, the halides can be further transformed into thiourea, pyridyl carboxamide, quinolyl sulfonamide compounds, some which show significant potential catalysis. Both experimental theoretical mechanistic studies support an halogen atom transfer mechanism. opens avenue accessing facilitating broad applications various related fields.

Language: Английский

Enantioselective synthesis of molecules with multiple stereogenic elements DOI Creative Commons
Arthur Gaucherand, Expédite Yen‐Pon,

Antoine Domain

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206

Published: Jan. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Language: Английский

Citations

12
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols DOI
Ping Wu,

Wen‐Tao Zhang,

Jixiang Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Language: Английский

Citations

9
Catalytic atroposelective synthesis of indolyl quinazolinones bearing N–N/C–C diaxes DOI

Ning‐Yi Wang,

Shuo Gao,

Zhiwei Shu

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Language: Английский

Citations

1
Asymmetric Construction of Functionalized Cyclopenta[b]pyrrolines via Cascade Aza-Piancatelli/Hydroamination Reactions DOI

Xukun Nie,

Sishi Zhong,

Jiaming Zou

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6766 - 6770

Published: July 31, 2024

A chiral Brønsted acid/Pd that cooperatively catalyzed the asymmetric cascade aza-Piancatelli rearrangement/hydroamination of readily accessible alkynyl-functionalized tertiary furylcarbinols with anilines has been developed. This protocol provides expedient access to a variety densely functionalized cyclopenta[b]pyrroline derivatives in high yields excellent enantioselectivities.

Language: Английский

Citations

4
Stereoselective Synthesis of Atropisomeric Amides Enabled by Intramolecular Acyl Transfer DOI Creative Commons
Jack M. Wootton,

Natalie J. Roper,

C. Morris

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A stereoselective strategy to make C–N atropisomeric amides based on intramolecular acyl transfer via a tethered Lewis basic pyridine or tertiary amine group is reported.

Language: Английский

Citations

0
Asymmetric Organocatalytic 1,6-Conjugate Addition of Alkynyl 8-Methylenenaphthalen-2(8H)-one Formed In Situ: Synergistic Construction of Axial and Central Chirality DOI

Meiwen Liu,

Yihao Zhang,

Xin-Yan Ke

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 26, 2025

Organocatalytic enantioselective formal nucleophilic substitution reactions of α-(2-hydroxynaphthalen-8-yl)propargyl alcohols with 1-(1H-indol-3-yl)naphthalen-2-ols have been established for the first time. With aid a suitable chiral phosphoric acid, alkynyl 8-methylenenaphthalen-2(8H)-one was formed in situ from corresponding alcohol, followed by 1,6-conjugate additions to afford number enantioenriched (Ra,Sc)-2,3-disubstituted indoles 50-80% yields 81-93% ee and (Sa,Sc)-2,3-disubstituted 18-40% 79-96% ee. Notably, these products were characterized presence functional groups, including indole, naphthol, units, while exhibiting both axial central chirality.

Language: Английский

Citations

0
Lewis Acid-Enabled Chemodivergent Cycloadditions of Donor–Acceptor Cyclopropanes with Indoline-2-Thiones DOI

Chen-Ying Zhai,

Bing Zhao, Xuelong Wang

et al.

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

Published: Feb. 20, 2025

Lewis acid-enabled reactions of donor-acceptor cyclopropanes (DACs) with indoline-2-thiones are reported. The reaction exhibits tunable annulation depending on the acid and substituent at N1 indoline-2-thiones. With AlCl3 as 1-isopropylindoline-2-thiones reactants, a direct ring opening DACs, followed by intramolecular nucleophilic addition/dehydration takes place leading to formation dihydro-2H-thiepino[2,3-b]indoles in moderate good yields. Using Yb(OTf)3 promoter 1-unsubstituted (3 + 2) cycloaddition DACs accompanied sulfur rearrangement give 3-indolyl-4,5-dihydrothiophenes In addition, synthetic transformation 3-indolyl-4,5-dihydrothiophene sulfone indole-based axially chiral scaffolds further extends utility structural complexity.

Language: Английский

Citations

0
Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines DOI

Junsoo Moon,

Eun Joo Shin, Yongseok Kwon

et al.

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

Published: April 5, 2025

Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration asymmetric catalysis. While the dual-catalytic approach led to successful examples of control stereogenic centers, axes remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, symmetric substrate, 2-arylresorcinol, desymmetrized aid chiral phosphoric acid Using approach, center axis were successfully controlled provide natural-product-driven compound. The origins enantioselectivity diastereoselectivity investigated density functional theory study four possible enantiodetermining transition states. Consequently, first total syntheses ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A B accomplished concisely. This provides not only novel methodology strategy synthesize alkaloids but also direction advance catalytic research synthesis studies.

Language: Английский

Citations

0
Development of Eagle‐Shaped BPE/Phe‐2NO Ligands: Switch of Enantioselectivity in Friedel–Crafts Alkylation DOI
Jun Young Yang,

Jing Lou,

Wei Li

et al.

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Abstract The development of single chiral source‐derived ligands to fine‐switch enantioselectivity has been a key aspect in asymmetric catalysis. Herein, this study, using the same source l ‐prolinamide as starting material, we synthesize 14 new diphenyl ether bridged C 2 ‐symmetric rigid tertiary amine‐derived dioxide (abberviated BPE‐2NO) and 9 m ‐phenylene Phe‐2NO); their effectiveness was demonstrated first switch palladium(II)‐catalyzed Friedel–Crafts alkylation. In presence palladium acetate Lewis acid, both enantiomers indole derivatives can be prepared good‐to‐excellent yields enantioselectivities by Eagle‐shaped BPE/Phe‐2NO ligands. Control experiments density functional theory calculations provide rational explanation for above observations. This study alkylation

Language: Английский

Citations

0
Catalytic Atroposelective Construction of Furan‐Based Axially Chiral Scaffolds DOI

Wei Tan,

Xinyue Wu, Feng Shi

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(21)

Published: July 19, 2024

Abstract Axially chiral furan‐based scaffolds have been recognized as a class of important five‐membered heteroaryl atropisomers, and developing catalytic atroposelective reactions for constructing this is highly desirable. However, the construction such rather underdeveloped due to existence great challenges remote ortho ‐substituents weak configurational stability. To overcome these challenges, synthetic chemists recently paid attention research field, number axially constructed via using different strategies. This concept summarized advances in field pointed out remaining which will promote further development emerging field.

Language: Английский

Citations

2