Stereospecific 3‐Aza‐Cope Rearrangement Interrupted Asymmetric Allylic Substitution‐Isomerization DOI Open Access

H.D. Zhuang,

Jun Gu,

Zhiwen Ye

et al.

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

Published: Oct. 17, 2024

Abstract Transition‐metal catalyzed asymmetric allylic substitution with alkyl and heteroaryl carbon nucleophiles has been well‐established. However, the arylation of acyclic internal alkenes aryl remains challenging underdeveloped. Herein we report a stereospecific 3‐aza‐Cope rearrangement interrupted substitution‐isomerization ( Int‐AASI ) that enables arylation. By means this stepwise strategy, both enantioenriched products axially chiral could be readily obtained in high enantioselectivities. Experimental studies support mechanism involving cascade amination, alkene isomerization. Density functional theory detailed reasons achieving chemoselectivity, regioselectivity, stereoselectivity stereospecificity, respectively.

Language: Английский

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

Citations

120
Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

Citations

42
Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination DOI
Wei Wang, Mingwei Jiang, Junwei Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16567 - 16580

Published: June 7, 2024

Axially chiral biaryls featuring a C–N axis are important functional molecules in diverse fields. The asymmetric Buchwald–Hartwig reaction represents powerful strategy for these targets. Previous studies, however, have been predominantly restricted to intramolecular atroposelective coupling, likely due the steric and entropic effects reductive elimination of Pd(II) species with sterically congested aryl nitrogen groups. We now report two intermolecular coupling systems bulky NH lactams halohydrocarbons enabled by rerouting mechanism one that accommodates challenging substrates. Both exhibited group tolerance, excellent enantioselectivity, high Z selectivity (if applicable), affording atropisomeric biaryl olefins through de novo construction axis. Experimental computational studies were performed elucidate mechanism, switch pathways is traced effect (ortho substituent) halide substrate. A 2,6-disubstituted reorients proximal lactamide ligand its unusual O-ligation mode. With amide oxygen participation, this intermediate undergoes an accessible barrier five-membered ring transition state, pathway as well induction mode has much underexplored catalysis.

Language: Английский

Citations

6
Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers DOI

Yulong Kang,

Fen Wang, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13055 - 13064

Published: Aug. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Language: Английский

Citations

5
Multiple Atropo Selectivity by κ2‐N,O‐Oxazoline Urea Ligands in Cobaltaelectro‐Catalyzed C─H Activations: Decoding Selectivity with Data Science Integration DOI Creative Commons
Philipp Boos, Neeraj Kumar Pandit, Suman Dana

et al.

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Enantioselective catalysis is one of the most prominent strategies in organic synthesis to access chiral bioactive compounds and advanced materials. Particularly, development ligands has significantly efficiency selectivity transition metal‐catalyzed enantioselective transformations. Over recent decades, numerous ligand classes with distinct geometrical electronic properties have been established. Despite these advances, demand for novel, tunable, highly effective persists, driven by need structurally diverse molecules pursuit greener, more sustainable catalytic processes. Herein, a novel class oxazoline ureas introduced their potential as κ 2 ‐ N , O ‐preligands metal demonstrated. The urea are featurized compared amide enol derivatives using physical descriptors. A multivariate linear regression model constructed quantitatively describe effect quinoline fragment from substrate on enantioselectivity. Moreover, effectively applied atropo‐enantioselective cobaltaelectro‐catalyzed C─H annulations 1‐alkynyl indoles.

Language: Английский

Citations

0
Rhodium(I)‐Catalyzed Asymmetric Hydroarylative Cyclization of 1,6‐Diynes to Access Atropisomerically Labile Chiral Dienes DOI
Panjie Hu,

Lingfei Hu,

Xiao‐Xi Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 16, 2023

Abstract Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization 1,6‐diynes with three distinct classes arenes, enabling highly broad range axially 1,3‐dienes that conformationally labile (Δ G ≠ ( rac )=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies the quinoline N ‐oxide system reveal proceeds via initial oxidative 1,6‐diyne give rhodacyclic intermediate, followed by σ‐bond metathesis between arene C−H bond Rh−C(vinyl) bond, subsequent C−C reductive elimination being enantio‐determining turnover‐limiting. DFT‐established mechanism is consistent experimental studies. coupled products ‐oxides undergo facile visible light‐induced intramolecular oxygen‐atom transfer, affording epoxides complete axial‐to‐central chirality transfer.

Language: Английский

Citations

8
Half-Sandwich d6-Metal (CoIII, RhIII, IrIII, RuII)-Catalyzed Enantioselective C–H Activation DOI Creative Commons
Pu‐Fan Qian, Jun-Yi Li, Yibo Zhou

et al.

SynOpen, Journal Year: 2023, Volume and Issue: 07(04), P. 466 - 485

Published: Sept. 6, 2023

Abstract Transition-metal-catalyzed enantioselective C–H activation provides a straightforward strategy to synthesize chiral molecules from readily available sources. In this graphical review, we summarize the progress on half-sandwich d6-metal (CoIII, RhIII, IrIII, RuII)-catalyzed functionalization reactions. The review is categorized according type of metal catalyst and ligand employed. Representative enantio-determining models catalytic cycles are presented.

Language: Английский

Citations

7
Progress in Asymmetric Catalytic Synthesis of C—N Axis Chiral Compounds DOI Open Access
Wanting Chen, Xiongwei Zhong, Jiale Xing

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(2), P. 349 - 349

Published: Jan. 1, 2024

Enantioenriched C-N axial chiral compounds are ubiquitous in many important field, such as natural products, drugs and ligands.Therefore, efficient construction of axis chirality through asymmetric catalytic synthesis has attracted more attention research interest.In this review, the recent progress been discussed, mainly from three aspects: desymmetrization prochiral molecules or kinetic resolution racemates, atroposelective functionalization axis, coupling reaction.The topic focuses on evolution system key factors control.The existing problems future development direction field also discussed.This paper is a timely systematic review will stimulate extensive interest.

Language: Английский

Citations

2
Catalytic Atroposelective Synthesis of N–N Axially Chiral Indolylamides DOI Creative Commons

Tian‐Zhen Li,

Shufang Wu,

Ning‐Yi Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12559 - 12575

Published: Aug. 27, 2024

The catalytic atroposelective synthesis of N–N axially chiral indolylamides was established via dynamic kinetic resolution, which makes use Lewis base-catalyzed asymmetric acylation N-acylaminoindoles as a new type platform molecule with anhydrides. By this strategy, series were synthesized in overall good yields (up to 98%) excellent enantioselectivities 99% ee). Moreover, some these display extent anticancer activity, demonstrates their potential application medicinal chemistry. Therefore, work has not only provided strategy for the monoaryl indoles but also offered member configurational stability and promising application, thereby solving challenges indoles.

Language: Английский

Citations

2
Plausible PEPPSI catalysts for direct C-H functionalization of furans and pyrroles DOI

Naima Munir,

Nevın Gürbüz,

M. Naveed Zafar

et al.

Journal of Molecular Structure, Journal Year: 2023, Volume and Issue: 1295, P. 136679 - 136679

Published: Sept. 19, 2023

Language: Английский

Citations

6