Recent advancements in the Ullmann homocoupling reaction for the synthesis of biaryl compounds DOI
Saima Perveen, Guoxiang Zhang, Pengfei Li

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In the realm of biaryl synthesis, Ullmann homocoupling reaction is a fundamental process for constructing compounds and has historically been driven by copper catalysis. However, significant studies have made in Ullmann-type coupling reactions, particularly formation structures, leading to more sustainable efficient synthetic pathways. Recent research concentrated on devising innovative catalytic systems, including palladium, gold, nickel nanoparticles, bimetallic species, surmount limitations conventional catalysts. These advancements broadened range substrates enhanced efficiency under gentler conditions, line with principles green chemistry. Mechanistic instrumental these developments, focusing nonchain single-electron transfer (SET) mechanism. Additionally, use recyclable heterogeneous catalysts mitigated stringent conditions associated original reaction. As continues evolve, asymmetric anticipated become key tool synthesis complex natural products heterocyclic systems pertinent medicinal This review aims cover recent developments compounds.

Language: Английский

Nickel‐Catalyzed Asymmetric Reductive Carbo‐Carboxylation of Alkenes with CO2 DOI
Xiao‐Wang Chen, Jun‐Ping Yue,

Kuai Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 14068 - 14075

Published: April 1, 2021

Abstract Reductive carboxylation of organo (pseudo)halides with CO 2 is a powerful method to provide carboxylic acids quickly. Notably, the catalytic reductive carbo‐carboxylation unsaturated hydrocarbons via fixation highly challenging but desirable approach for structurally diverse acids. There are only few reports and no examples alkenes transition metal catalysis. We report first asymmetric nickel A variety aryl (pseudo)halides, such as bromides, triflates inert chlorides particular note, undergo reaction smoothly give important oxindole‐3‐acetic acid derivatives bearing C3‐quaternary stereocenter. This transformation features mild conditions, wide substrate scope, facile scalability, good excellent chemo‐, regio‐ enantioselectivities. The highlights formal synthesis (−)‐Esermethole, (−)‐Physostigmine (−)‐Physovenine, total (−)‐Debromoflustramide B, (−)‐Debromoflustramine B (+)‐Coixspirolactam A; thereby, opening an avenue chiral natural products .

Language: Английский

Citations

108
Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction DOI
Dong Liang, Jia‐Rong Chen, Liping Tan

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 6040 - 6049

Published: March 24, 2022

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged ligand/catalysts, optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable intriguing strategy but are far less developed. Moreover, efficient synthesis axially heterobiaryl molecules, especially ones having multiple heteroatoms other types elements, through radical routes remains extremely limited. We herein disclose first catalytic asymmetric, metal-free construction centrally by Minisci reaction 5-arylpyrimidines α-amino acid-derived redox-active esters. This is enabled use 4CzIPN as an organic photoredox catalyst conjunction a phosphoric acid catalyst. The achieved variety interesting featuring union α-branched amine generally excellent regio-, diastereo-, enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). finding also builds up new platform development desymmetrization methods via radical-involved atroposelective functionalization at heteroarene prochiral heterobiaryls.

Language: Английский

Citations

78
Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications DOI Creative Commons
Xiaopeng Peng, Abdur Rahim, Weijie Peng

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1364 - 1416

Published: Jan. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Language: Английский

Citations

71
Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES) DOI
Cong Ma, Jianfeng Guo,

Shi-Shuo Xu

et al.

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

Published: Jan. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Language: Английский

Citations

3
Synthesis of Axially Chiral 2,2′-Bisphosphobiarenes via a Nickel-Catalyzed Asymmetric Ullmann Coupling: General Access to Privileged Chiral Ligands without Optical Resolution DOI

Ziqing Zuo,

Raphael S. Kim, Donald A. Watson

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(3), P. 1328 - 1333

Published: Jan. 13, 2021

We report an asymmetric homocoupling of ortho-(iodo)arylphosphine oxides and ortho-(iodo)arylphosphonates resulting in highly enantioenriched axially chiral bisphosphine bisphosphonates. These products are readily converted to biaryl bisphosphines without need for auxiliaries or optical resolution. This provides a practical route the development previously uninvestigated atroposelective ligands. The conditions have also proven effective dimerization other, non-phosphorus-containing aryl halides.

Language: Английский

Citations

65
Enantioselective Rh-Catalyzed Azide-Internal-Alkyne Cycloaddition for the Construction of Axially Chiral 1,2,3-Triazoles DOI
Wenting Guo,

Bo‐Han Zhu,

Yi Chen

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(15), P. 6981 - 6991

Published: April 8, 2022

Significant advances have been achieved for the construction of chiral skeletons containing 1,2,3-triazoles via transition-metal-catalyzed asymmetric azide–alkyne cycloaddition; however, most them limited to terminal alkynes in synthesis central chirality desymmetrization and dynamic/dynamic kinetic resolution. Enantioselective azide-internal-alkyne cycloaddition is extremely limited. Moreover, a challenging five-membered (hetero)biaryl axially molecule still underexplored. Herein, we first report an atroposelective atom-economical 1,4,5-trisubstituted 1,2,3-triazoles, directly acting as core units atropisomers, enantioselective Rh-catalyzed (E-RhAAC) internal azides. The reaction demonstrates excellent functional group tolerance, forging variety C–C under mild conditions with moderate yields (up 99% yield) generally high enantioselectivities ee) along specific regiocontrol. origin regio- enantioselectivity control disclosed by density theory (DFT) calculations, providing new guidance facile compounds.

Language: Английский

Citations

57
2,2′‐Biphenol‐based Ultrathin Microporous Nanofilms for Highly Efficient Molecular Sieving Separation DOI
Shao‐Lu Li,

Guoliang Chang,

Yangzheng Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 23, 2022

Organic solvent nanofiltration (OSN) is an emerging membrane separation technology, which urgently requires robust, easily processed, OSN membranes possessing high permeance and small solutes-selectivity to facilitate enhanced industrial uptake. Herein, we describe the use of two 2,2'-biphenol (BIPOL) derivatives fabricate hyper-crosslinked, microporous polymer nanofilms through IP. Ultra-thin, defect-free polyesteramide/polyester (≈5 nm) could be obtained readily due relatively large molecular size ionized nature BIPOL monomers retarding rate The microporosity arises from hyper-crosslinked network structure monomer rigidity. Specifically, amino-BIPOL/PAN exhibits extraordinary permselectivity performances with weight cut-off as low 233 Da MeOH ≈13 LMH/bar. Precise dye mixtures similar M.W. based on both their charge are achieved.

Language: Английский

Citations

47
Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

16
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
Enantioselective Cobalt-Catalyzed Reductive Cross-Coupling for the Synthesis of Axially Chiral Phosphine–Olefin Ligands DOI
Xi Zhang, Juan Wang, Shang‐Dong Yang

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(22), P. 14008 - 14015

Published: Nov. 4, 2021

Transition-metal-catalyzed enantioselective cross-electrophile coupling reactions to construct C(sp2)–C(sp2) bonds remain a challenge. Herein, we report general process for the Co-catalyzed reductive cross-coupling reaction of o-(bromo)arylphosphine oxide substrates and vinyl triflates, delivering axially chiral phosphine compounds with good chemo- enantioselectivity. A broad range was obtained excellent enantioselectivities, practical potential this catalyst system demonstrated by versatile formation ligands other functional atropisomers.

Language: Английский

Citations

46