Chiral sulfide and achiral sulfonic acid cocatalyzed enantioselective electrophilic tandem selenylation semipinacol rearrangement of allenols DOI Creative Commons

Ren‐Fei Cao,

Ruirui Su,

Zhiwei Wei

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 3, 2025

A highly enantioselective electrophilic selenylation/semipinacol rearrangement of allenols has been developed, which is enabled by the cooperative catalysis a chiral sulfide and an achiral sulfonic acid. The designed synthesized catalyst selenylating reagent play crucial role in enhancing both enantioselectivity reactivity. This approach exhibits excellent regio-, chemo-, enantioselectivity, providing access to diverse enantioenriched cyclopentanones featuring arylselenovinyl-substituted quaternary carbon stereocenter. Furthermore, these products can be transformed into synthetically valuable alkyne, vinyl bromide, aniline derivatives. Mechanistic studies reveal that combination acid not only facilitates formation catalytically active species, but also governs reaction. Meanwhile, density functional theory calculations disclose four hydrogen bond interactions π‧‧‧π interaction are responsible for observed enantioselectivity. Rearrangement reactions serve as steps syntheses biologically provide intellectual conceptual curiosities within broad field organic chemistry. Here, authors report allenols, catalysed Lewis base.

Language: Английский

Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation DOI

Bo Dong,

Jian Shen, Lan‐Gui Xie

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1322 - 1345

Published: Jan. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Language: Английский

Citations

66
Enantioselective Synthesis of Planar‐Chiral Sulfur‐Containing Cyclophanes by Chiral Sulfide Catalyzed Electrophilic Sulfenylation of Arenes DOI

Deng Zhu,

Tong Mu,

Ze‐Long Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 17, 2024

Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.

Language: Английский

Citations

18
Chalcogen bonding catalysis DOI
Govindasamy Sekar,

Vysakh Venugopalan Nair,

Jieping Zhu

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 586 - 605

Published: Dec. 7, 2023

Catalysts play a major role in chemical synthesis, and catalysis is considered to be green economic process. Catalysis dominated by covalent interactions between the catalyst substrate. The design of non-covalent catalysts came into limelight only recently. Hydrogen bonding (HB) are well established among catalysts, including asymmetric HB catalysts. Though halogen (XB) its version gaining admiration, chalcogen (ChB) budding stage. This tutorial review will focus on recently evolved emphasis given chiral molecules. Since successful enantioselective yet reported, this basics catalysis, chalcogenide rigidification transition states ChB, stabilization cations chalcogens, details unsuccessful enantioseparation racemic molecules using existence ChB biomolecules.

Language: Английский

Citations

31
Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles DOI

Zhichao Qi,

Yuke Li, Juan Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13301 - 13309

Published: Oct. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Language: Английский

Citations

29
Catalytic Enantioselective Aminative Difunctionalization of Alkenes DOI
Nan Huang, Jie Luo, Lihao Liao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 7029 - 7038

Published: March 1, 2024

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction enantioenriched complex molecules. Despite tremendous efforts devoted to this field, enantioselective aminative remains challenge, particularly through an electrophilic addition fashion. Herein, we report unprecedented approach via copper-catalyzed with external azo compounds as nitrogen sources. A series valuable cyclic hydrazine derivatives either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In transformation, wide range functional groups, such carboxylic acid, hydroxy, amide, sulfonamide, aryl could serve nucleophiles. Importantly, new cyano oxazoline chiral ligand was found play crucial role control enantioselectivity.

Language: Английский

Citations

12
Rh(III)-Catalyzed Atroposelective C–H Selenylation of 1-Aryl Isoquinolines DOI

Dong‐Song Zheng,

Pei‐Pei Xie,

Fangnuo Zhao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6009 - 6015

Published: April 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Language: Английский

Citations

12
Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides DOI

Yi-Xin Wang,

Jing-Run Wang,

Chen Cui

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060

Published: Feb. 20, 2025

Language: Английский

Citations

1
Atroposelective Sulfenylation of Biaryl Anilines Catalyzed by Chiral SPINOL-Derived Selenide DOI

Xin-Yu Zhang,

Deng Zhu,

Yu-Xuan Huo

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(19), P. 3445 - 3450

Published: May 11, 2023

The atroposelective electrophilic sulfenylation of biaryl anilines has been realized for the first time. reaction is enabled by a new chiral 6,6'-dianisole substituted SPINOL-derived selenide. A variety axially sulfur-containing aniline compounds were obtained in moderate to excellent yields with enantioselectivities. experimental results suggest that catalyst rigidity important high atroposelectivity.

Language: Английский

Citations

21
Versatile electrooxidative amino- and oxyselenation of alkenes DOI
R. Wang,

Nana Zhang,

Yonghong Zhang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(10), P. 3925 - 3930

Published: Jan. 1, 2023

We herein describe a methodology for the production of organoselenium compounds by electrocatalytic difunctionalisation alkenes.

Language: Английский

Citations

20
Copper(I)‐Catalyzed Conjugate Addition/Enantioselective Protonation with Selenols and α‐Substituted α,β‐Unsaturated Thioamides DOI
Hu Tian, Hongming Zhang, Liang Yin

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 22, 2023

Herein, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and α-substituted α,β-unsaturated thioamides is disclosed, which affords series of chiral selenides in high to excellent enantioselectivity. As for both thioamides, the reaction enjoys broad substrate scopes. The present catalytic system also successfully applied selenation β-substituted thioamides. A [Cu-(R,RP )-TANIAPHOS]-SePh species characterized by its 77 Se NMR spectra, gives chemical shift at δ 462 ppm. Moreover, {[Cu-(R)-TOL-BINAP]-SePh}2 X-ray analysis, confirms formation Cu-Se bond reaction. Finally, transformations thioamide group amine thioester are demonstrated be straightforward.

Language: Английский

Citations

18