Enantioselective Rh(I)-Catalyzed C–H Arylation of Ferroceneformaldehydes DOI Creative Commons
Chen‐Xu Liu,

Fangnuo Zhao,

Qing Gu

et al.

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(11), P. 2036 - 2043

Published: Sept. 28, 2023

As an important class of platform molecules, planar chiral ferrocene carbonyl compounds could be transformed into various functional groups offering facile synthesis ligands and catalysts. However, developing efficient straightforward methods for accessing enantiopure compounds, especially ferroceneformaldehydes, remains highly challenging. Herein, we report a rhodium(I)/phosphoramidite-catalyzed enantioselective C–H bond arylation ferroceneformaldehydes. Readily available aryl halides such as iodides, bromides, even chlorides are suitable coupling partners in this transformation, leading to series ferroceneformaldehydes good yields excellent enantioselectivity (up 83% yield >99% ee). The aldehyde group diverse smoothly, Ugi's amine PPFA analogues synthesized efficiently. latter was found ligand Pd-catalyzed asymmetric allylic alkylation reactions. Mechanistic experiments supported the formation imine intermediates key step during reaction.

Language: Английский

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling DOI
Yudong Yang, Yimin Wu, Zhengyang Bin

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1224 - 1243

Published: Jan. 4, 2024

Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are paramount importance in quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions between two (hetero)arenes have emerged as a concise effective approach generating wide array bi(hetero)aryl fused heteroaryl structures. This innovative bypasses challenges associated with substrate pre-activation processes, thereby allowing creation frameworks were previously beyond reach using conventional Ar–X/Ar–M reactions. These inherent advantages ushered new design patterns molecules deviate from traditional methods. ground-breaking enables transcendence limitations repetitive material structures, ultimately leading to discovery novel high-performance In this Perspective, we provide an overview recent advances development materials through utilization We introduce several notable strategies domain, covering both directed non-directed strategies, dual chelation-assisted strategy ortho-C–H arylation/cyclization strategy. Additionally, shed light on role advancement Finally, discuss current existing protocols offer insights into future prospects field.

Language: Английский

Citations

21
C–H activation-initiated spiroannulation reactions and their applications in the synthesis of spirocyclic compounds DOI

Qianting Zhou,

Bin Li, Xinying Zhang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(12), P. 2324 - 2338

Published: Jan. 1, 2024

This review summarizes the most recent progress made in C–H bond activation-initiated spiroannulation reactions and their applications construction of structurally diverse biologically valuable spirocyclic scaffolds.

Language: Английский

Citations

21
Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes DOI
Gang Zhou, Tao Zhou,

Ao‐Lian Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Language: Английский

Citations

20
Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development DOI
Qi‐Jun Yao, Bing‐Feng Shi

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Language: Английский

Citations

3
Rh(III)-Catalyzed [3 + 2] Annulation/Pinacol Rearrangement Reaction of Enaminones with Iodonium Ylides: Direct Synthesis of 2-Spirocyclo-pyrrol-3-ones DOI

Mingshuai Zhang,

Longkun Chen,

Haifeng Sun

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7214 - 7219

Published: Sept. 26, 2023

A novel Rh(III)-catalyzed cascade alkenyl C-H activation/[3 + 2] annulation/pinacol rearrangement reaction of enaminones with iodonium ylides has been developed. This methodology provides a new and straightforward synthetic strategy to afford highly functionalized 2-spirocyclo-pyrrol-3-ones in satisfactory yield from readily available starting materials under mild conditions. Moreover, gram-scale reactions further derivatization experiments are implemented demonstrate the potential utility this developed approach.

Language: Английский

Citations

33
Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions DOI
Zhuo‐Zhuo Zhang, Gang Zhou, Qiang Yue

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

Citations

16
Expedient Synthesis of Axially and Centrally Chiral Diaryl Ethers via Cobalt-Catalyzed Photoreductive Desymmetrization DOI
Yishou Wang,

Ruijie Mi,

Songjie Yu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4638 - 4647

Published: March 12, 2024

Axially chiral diaryl ethers make up a unique class of atropisomers bearing restricted rotation about the C–O bond. Methods for expedient synthesis axially ether-based structures have been largely underdeveloped. Herein, we developed an efficient metal-catalyzed desymmetrization strategy to unveil formation and centrally dual in high diastereo- enantioselectivity. The protocol leverages cobalt-catalyzed photoreductive enantioselective couplings dialdehyde alkyne deliver stereogenicity, ether scaffold is equipped with useful synthetic handles including formyl, hydroxyl, allyl groups, as has demonstrated carboxylic acid potential ligand asymmetric catalysis.

Language: Английский

Citations

16
Recent advances in Rh(i)-catalyzed enantioselective C–H functionalization DOI Creative Commons
Yue Zhang, Jing‐Jing Zhang, Lujun Lou

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3457 - 3484

Published: Jan. 1, 2024

Chiral carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds are pervasive very essential in natural products, bioactive molecules, functional materials, their catalytic construction has emerged as one of the hottest research fields synthetic organic chemistry. The last decade witnessed vigorous progress Rh(I)-catalyzed asymmetric C-H functionalization a complement to Rh(II) Rh(III) catalysis. This review aims provide most comprehensive up-to-date summary covering recent advances activation for functionalization. In addition development diverse reactions, chiral ligand design mechanistic investigation (inner-sphere mechanism, outer-sphere 1,4-Rh migration) will also be highlighted.

Language: Английский

Citations

14
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

13
Enantioselective Rhodium‐Catalyzed C−H Arylation Enables Direct Synthesis of Atropisomeric Phosphines DOI
Zexian Li,

Weipeng Xu,

Shuaishuai Song

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 6, 2024

Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, groundbreaking methodology has been presented for preparation. This innovative approach entails an atroposelective rhodium-catalyzed C-H activation employing aryl and heteroaryl halides, chelated by P(III) center. The essence of strategy lies its ability directly construct chiral phosphine ligands single step, thereby exhibiting exceptional efficiency terms atom redox economy. Illustrative examples serve demonstrate the immense potential situ-formed catalysis. Mechanistic experiments have further provided invaluable insights into transformation.

Language: Английский

Citations

10