Secondary Cationic Interaction Driven Substrate Ligand Affinity for Pd(II)-Catalyzed Enantioselective C-H Activation of Ferrocenyl Amines DOI Creative Commons
Devendra Parganiha, Raviraj Ananda Thorat, Ashwini Dilip Dhumale

et al.

Published: July 29, 2024

Secondary amines as a directing group for C-H activation have limitations they are prone to undergo oxidation, allylic deamination, and β-hydride elimination. The fundamental challenge observed here is the competition between desired versus vulnerable β-C-H bond of secondary amine when substrate ligand affinity not strong enough. Herein, potential axially chiral NOBINAc revealed accelerate enantioselective PdII-catalyzed process ferrocenyl amines. Further, interaction cesium cation with sulfonate plays an impressive role in mitigating threat elimination via enhanced affinity. This approach resulted activation, intermolecular annulation, alkenylation allenes activated olefines, leading ferrocene fused tetrahydropyridines alkenylated up 70% yields 99:1 er.

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

118
Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization DOI Creative Commons
Yang Zheng, Wenyun Zhang, Qing Gu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Feb. 25, 2023

Abstract Asymmetric ring-opening of 7-oxabenzonorbornadienes is achieved via Co-catalyzed indole C–H functionalization. The utilization chiral Co-catalyst consisting a binaphthyl-derived trisubstituted cyclopentadienyl ligand resulted in high yields (up to 99%) and excellent enantioselectivity (>99% ee) for the target products with tolerance diverse functional groups. Opposite diastereoselectivities are obtained or Cp*CoI 2 CO. Combined experimental computational studies suggest β -oxygen elimination being selectivity-determining step reaction. Meanwhile, reactions 7-azabenzonorbornadiene could also be executed diastereodivergent manner.

Language: Английский

Citations

31
Iridium-Catalyzed Regiodivergent Atroposelective C–H Alkylation of Heterobiaryls with Alkenes DOI

Maoqian Xiong,

Zilong Yan,

Si‐Cong Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7243 - 7255

Published: April 24, 2024

The atroposelective direct C–H alkylation of heterobiaryls with simple alkenes represents a challenging and underexplored frontier. Herein we report an iridium(I)-catalyzed regiodivergent enantioselective 1-arylisoquinolines or 2-arylpyridines alkenes. By utilizing cationic iridium catalyst different types chiral bidentate phosphine ligands, both linear- branched-selective alkylations were achieved high regioselectivities enantioselectivities. With this atom-economic ligand-enabled protocol, series axially nitrogen-containing synthesized good efficiency enantioselectivity. For the linear-selective involving styrene moiety, computational investigations illuminated that regioselectivity is established during migratory insertion step into Ir–C bond. Both experimental density functional theory (DFT) studies concerning substituent effects moiety also conducted. These results suggest primacy role resonance effect relative to field-inductive in determining transformation.

Language: Английский

Citations

10
Enantioselective synthesis of indenols via rhodium(III)–catalyzed C-H activation/annulation of ketones with alkynes DOI

Bo-Bo Gou,

Wenjie Shen, Yuanjun Gao

et al.

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

Published: Feb. 12, 2025

Language: Английский

Citations

1
(SCp)Rhodium‐Catalyzed Asymmetric Satoh–Miura Reaction for Building‐up Axial Chirality: Counteranion‐Directed Switching of Reaction Pathways DOI
Wenwen Zhang, Qiang Wang,

Suzhen Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Nov. 16, 2022

Satoh-Miura reaction is an important method for extending π-systems by forging multi-substituted benzene rings via double aryl C-H activation and annulation with alkynes. However, the development of highly enantioselective remains rather challenging. Herein, we report asymmetric between 1-aryl benzo[h]isoquinolines internal alkynes enabled a SCpRh-catalyst. Judiciously choosing counteranion Rh-catalyst crucial desired reactivity over competitive formation azoniahelicenes. Detailed mechanistic studies support proposal counteranion-directed switching pathways in Rh-catalyzed activation.

Language: Английский

Citations

38
Rhodium-catalyzed annulative approach to N–N axially chiral biarylsviaC–H activation and dynamic kinetic transformation DOI Creative Commons
Xiaohan Zhu, Hongli Wu, Yishou Wang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(32), P. 8564 - 8569

Published: Jan. 1, 2023

N-N axially chiral biaryls represent a rarely explored class of atropisomeric compounds. We hereby report rhodium-catalyzed enantioselective [4 + 2] oxidative annulation internal alkynes with benzamides bearing two classes directing groups. The coupling occurs under mild conditions

Language: Английский

Citations

18
Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles DOI

Hongxuan Zhai,

Kang Lv, Jiayan Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 29214 - 29223

Published: Oct. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Language: Английский

Citations

8
Synthesis of Hexamethyl-1,1′-spirobiindane-Based Chiral Spiro Cp Ligands and Their Application in Rhodium-Catalyzed Enantioselective Aryl C–H Addition to Nitroalkenes DOI
Hui Yang, Ru Zhang,

Suzhen Zhang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8838 - 8844

Published: June 20, 2023

Spiro cyclopentadienyl rhodium (SCpRh) complexes are powerful catalysts for promoting asymmetric C–H functionalization reactions. However, the application of chiral SCp ligands is limited due to tedious synthetic procedures and expensive starting materials. Herein, we have developed a series spiro (BCSCp) with 6–7 steps from commercially available cheap Bisphenol C. Their corresponding been prepared successfully applied in enantioselective aryl addition nitroalkenes, affording adducts up 88% yield 98% ee.

Language: Английский

Citations

15
Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands DOI Creative Commons
Xin Kuang,

Jian-Jun Li,

Tao Liu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 24, 2023

A wide range of Cu(II)-catalyzed C-H activation reactions have been realized since 2006, however, whether a metalation mechanism similar to Pd(II)-catalyzed reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated reactions, realizing the enantioselective version investigating critically important. With modified chiral BINOL ligand, we report first example Cu-mediated for construction planar ferrocenes with high yields stereoinduction. The key success discovery acceleration effect BINOL-based diol in directed Cu-catalyzed alkynylation ferrocene derivatives bearing oxazoline-aniline directing group. This transformation compatible terminal aryl alkyl alkynes, which are incompatible Pd-catalyzed reactions. finding provides invaluable mechanistic information determining Cu(II) cleaves bonds via CMD pathway analogous manner Pd(II) catalysts.

Language: Английский

Citations

13
Molecularly Selective Polymer Interfaces for Electrochemical Separations DOI
Nayeong Kim, Wangsuk Oh, Kyle N. Knust

et al.

Langmuir, Journal Year: 2023, Volume and Issue: 39(47), P. 16685 - 16700

Published: Nov. 13, 2023

The molecular design of polymer interfaces has been key for advancing electrochemical separation processes. Precise control interactions at enabled the removal or recovery charged species with enhanced selectivity, capacity, and stability. In this Perspective, we provide an overview recent developments in applied to liquid-phase separations, a focus on their role as electrosorbents well membranes electrodialysis systems. particular, delve into both single-site macromolecular redox polymers use heterogeneous platforms. We highlight significance incorporating redox-active non-redox-active moieties tune binding toward ever more challenging including structurally similar even isomers. Furthermore, discuss advances development selective ion-exchange critical need physicochemical properties polymer. Finally, share perspectives challenges opportunities ranging from comprehensive understanding mechanisms continued innovation architectures electrodes.

Language: Английский

Citations

12