Harnessing Dpp-Imine as a Powerful Achiral Cocatalyst to Dramatically Increase the Efficiency and Stereoselectivity in a Magnesium-Mediated Oxa-Michael Reaction DOI Creative Commons

Yingfan Xu,

Dan Liu,

Feiyun Gao

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 4(1), P. 164 - 176

Published: Dec. 21, 2023

Dpp-imines are classic model substrates for synthetic method studies. Here, we disclose their powerful use as achiral coligands in metal-catalyzed reactions. It is highly interesting to find that the Dpp-imine can not only act ligand create excellent chiral pockets with magnesium complexes but also, more importantly, this coligand dramatically enhance catalytic ability of metal catalyst. The underlying reaction mechanism was extensively explored by conducting a series experiments, including

Language: Английский

Organocatalytic diastereo- and atroposelective construction of N–N axially chiral pyrroles and indoles DOI Creative Commons
Shaojie Wang, Xia Wang,

Xiaolan Xin

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 15, 2024

Abstract The construction of N–N axially chiral motifs is an important research topic, owing to their wide occurrence in natural products, pharmaceuticals and ligands. One efficient method the atroposelective dihydropyrimidin-4-one formation. We present herein a direct catalytic synthesis atropisomers with simultaneous creation contiguous axial central chirality by oxidative NHC ( N -heterocyclic carbenes) catalyzed (3 + 3) cycloaddition. Using our method, we are able synthesize structurally diverse pyrroles indoles vicinal or bearing 2,3-dihydropyrimidin-4-one moiety moderate good yields excellent enantioselectivities. Further synthetic transformations obtained derivative products demonstrated. reaction mechanism origin enantioselectivity understood through DFT calculations.

Language: Английский

Citations

29
Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene DOI Creative Commons

Yuxing Cai,

Yuxin Zhao,

Kai Tang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 12, 2024

Abstract We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with squaramide as hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via unique amide C–N bond cleavage mode. The free species attacks carbonyl, forming axially chiral acyl-azolium intermediate. Various amines be accessed by this methodology up to 99% ee and yield. By using mercaptan catalyst turnover agent, resulting thioester synthon transformed into several interesting atropisomers. Both control experiments theoretical calculations reveal crucial role hybrid NHC-HBD skeleton, activates H-bonding brings it spatially close centre. This discovery illustrates potential chimera demonstrates complementary strategy for activation manipulation.

Language: Английский

Citations

17
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
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
Asymmetric Aminative Dearomatization of 2-Naphthols via Non-covalent N-Heterocyclic Carbene Catalysis DOI

Ujjwal Maji,

Bhaskar Mondal, Joyram Guin

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2323 - 2327

Published: March 30, 2023

Herein, successful utilization of non-covalent N-heterocyclic carbene (NHC) catalysis toward asymmetric aminative dearomatization naphthols is presented. The NHC-catalyzed process offers enantioselective synthesis cyclic enones possessing a nitrogen-containing α-quaternary stereocenter. reaction applies to various functionalized substrates including acid-labile groups and shown be scalable. Substrate activation via an O-H···NHC hydrogen-bonding interaction suggested based on the results obtained in mechanistic studies.

Language: Английский

Citations

17
Metal-Free Enantioselective 1,4-Addition of Diarylphosphine Oxides to α,β-Unsaturated Carboxylic Esters DOI

Guangfu Lu,

Liangrui Xiao,

Qitao Que

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7573 - 7578

Published: May 23, 2024

The catalytic asymmetric conjugate addition of phosphorus nucleophiles to unsaturated compounds, catalyzed by metallic or nonmetallic catalysts, has been extensively developed. However, the enantioselective transformations involving α,β-unsaturated carboxylic esters for constructing chiral c-p bonds have rarely reported, particularly in metal-free processes. In this study, we present a novel methodology 1,4-addition diarylphosphine oxides using classical oxazaborolidine catalysts. Remarkably high yields and enantioselectivities were obtained most products. Furthermore, these valuable serve as crucial intermediates that can be transformed into various derivatives including amides, acids, alcohols single step.

Language: Английский

Citations

5
Carbene-catalyzed enantioselective seleno-Michael addition as access to antimicrobial active Se-containing heterocycles DOI

Hongyan Long,

Sha Zhao,

Chunyan Jian

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(7), P. 2199 - 2205

Published: May 28, 2024

Language: Английский

Citations

5
Copper(I)-Catalyzed Asymmetric α-Selenenylation of 2-Acylimidazoles DOI Creative Commons
Hu Tian, Xiaoyu Huang,

Jun‐Zhao Xiao

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 578 - 585

Published: Jan. 21, 2025

A general method for the catalytic asymmetric α-selenenylation of simple carbonyl compounds is lacking. Herein, a copper(I)-catalyzed enantioselective 2-acylimidazoles with electrophilic selenosulfonates uncovered. The reaction enjoys advantages mild conditions, easy protocol, and broad substrate scopes on both selenosulfonates. Mechanistic studies reveal pincer Cu(I)-(S,S)-Ph-BOPA complex as active catalyst. Some traditional selenenylation reagents, such PhSeCl, PhSeSePh, 2-(phenylselanyl)isoindoline-1,3-dione lead to inferior results in terms yield enantioselectivity, highlighting superiority Finally, several transformations based 2-acylimidazole group selenoether are successfully carried out, demonstrating synthetic utilities present methodology.

Language: Английский

Citations

0
Bifunctional NHC-Catalyzed Asymmetric Intramolecular Conjugate Addition via Noncovalent Interaction DOI

Ujjwal Maji,

Arpita Baidya,

Supriyo Das

et al.

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

Published: Feb. 28, 2025

Herein, we report a novel squaramide containing chiral bifunctional N-heterocyclic carbene (NHC) and its utilization in developing asymmetric intramolecular conjugate addition involving noncovalent interaction. Via concomitant activation of both electrophilic nucleophilic centers substrates, the reaction proceeds through well-organized transition state, thereby affording products with up to 94% ee broad scope. The process is found be scalable. initial mechanistic study supports nature newly designed NHC.

Language: Английский

Citations

0
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

Citations

0