Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

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

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Atroposelective Synthesis of C–C Axially Chiral Compounds via Mono- and Dinuclear Vanadium Catalysis

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(20), P. 2949 - 2965

Published: Oct. 7, 2022

ConspectusAxially chiral compounds with rotationally constrained σ-bonds that exhibit atropisomerism are lucrative synthetic targets because of their ubiquity in functional materials and natural products. The metal complex-catalyzed enantioselective fabrication axially scaffolds has been widely investigated, thus far, considerable progress made. Over the past two decades, we have developed a highly efficient strategy for constructing biarenol derivatives using mono- dinuclear vanadium complexes. These complexes readily prepared from vanadium(IV) salts Schiff base ligands (generated condensation (S)-tert-leucine di- or monoformyl-(R)-1,1′-bi-2-naphthol (BINOL) derivatives) under O2 act as active catalysts stereoselective C–C bond formation. In particular, oxidative coupling 2-naphthols 1 oxygen air, which is green oxidant, affords desired molecules high yields stereoselectivity (up to quantitative yield 97% ee), along water sole coproduct. This reaction tolerated various groups (such halogens, alkoxys, boryls) avoided overoxidation products.The key feature vanadium(V) such (Ra,S,S)-5a an outstanding mode homocoupling reaction, single molecule catalyst activates starting material (e.g., 2-naphthols) simultaneously. With this "dual activation" mechanism, promoted by proceeds intramolecular manner. rate 5 mol % complex was measured be 111 times faster than mononuclear (S)-4a bearing half motif complex.In case heterocoupling utilizing different kinds arenol derivatives, only having lower oxidation potential seems activated complex. either showed no difference give product but manner; better enantioselectivites A competing study linear correlation between ee mononucaler suggested involves intermolecular radical-anion pathway.In Account, summarize recent advances vanadium-catalyzed reactions produced important molecules, biresorcinols, polycyclic biphenols, oxa[9]helicenes, bihydroxycarbazoles, C1-symmetrical biarenols, mechanisms. By pursuing catalysis, believe numerous additional transformations well renewed interest catalytic chemo-, regio-, aryl–aryl constructions will manifested.

Language: Английский

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The Mechanochemical Synthesis and Activation of Carbon‐Richπ‐Conjugated Materials

Advanced Science, Journal Year: 2022, Volume and Issue: 9(19)

Published: Jan. 20, 2022

Mechanochemistry uses mechanical force to break, form, and manipulate chemical bonds achieve functional transformations syntheses. Over the last years, many innovative applications of mechanochemistry have been developed. Specifically for synthesis activation carbon-rich π-conjugated materials, offers reaction pathways that either are inaccessible with other stimuli, such as light heat, or improve yields, energy consumption, substrate scope. Therefore, this review summarizes recent advances in research field combining viewpoints polymer trituration mechanochemistry. The highlighted mechanochemical include materials optical probes, force-induced release small dye molecules, polyacetylene, carbon allotropes, materials.

Language: Английский

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Enantioselective synthesis of atropisomeric indoles via iron-catalysed oxidative cross-coupling

Nature Chemistry, Journal Year: 2022, Volume and Issue: 15(3), P. 357 - 365

Published: Dec. 12, 2022

Language: Английский

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A General, Multimetallic Cross-Ullmann Biheteroaryl Synthesis from Heteroaryl Halides and Heteroaryl Triflates

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(51), P. 21484 - 21491

Published: Dec. 17, 2021

Despite their importance to medicine and materials science, the synthesis of biheteroaryls by cross-coupling remains challenging. We describe here a new, general approach biheteroaryls: Ni- Pd-catalyzed multimetallic cross-Ullmann coupling heteroaryl halides with triflates. An array 5-membered, 6-membered, fused bromides chlorides, as well aryl triflates derived from heterocyclic phenols, proved be viable substrates in this reaction (62 examples, 63 ± 17% average yield). The generality was further demonstrated 96-well plate format at 10 μmol scale. 96 possible products provided >90% hit rate under single set conditions. Further, low-yielding combinations could rapidly optimized "Toolbox Plate" ligands, additives, reductants.

Language: Английский

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Atroposelective synthesis of biaxial bridged eight-membered terphenyls via a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization of phenols

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

Published: May 30, 2024

Abstract Bridged chiral biaryls are axially compounds with a medium-sized ring connecting the two arenes. Compared plentiful methods for enantioselective synthesis of biaryl compounds, synthetic approaches this subclass bridged atropisomers limited. Here we show an atroposelective 1,3-diaxial eight-membered terphenyl through Co/SPDO (spirocyclic pyrrolidine oxazoline)-catalyzed aerobic oxidative coupling/desymmetrization reaction prochiral phenols. This catalytic desymmetric process is enabled by combination earth-abundant Co(OAc) 2 and unique SPDO ligand in presence DABCO (1,4-diaza[2.2.2]bicyclooctane). An array diaxial terphenyls embedded azocane can be accessed high yields (up to 99%) excellent enantio- (>99% ee) diastereoselectivities (>20:1 dr).

Language: Английский

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Characterization and Reactivity of Copper(II) and Copper(III) σ-Aryl Intermediates in Aminoquinoline-Directed C–H Functionalization

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18253 - 18259

Published: Aug. 8, 2023

Over the past decade, numerous reports have focused on development and applications of Cu-mediated C-H functionalization reactions; however, to date, little is known about Cu intermediates involved in these transformations. This paper details observation characterization CuII CuIII aminoquinoline-directed C(sp2)-H a fluoroarene substrate. An initial activation at occurs room temperature afford an isolable anionic cyclometalated complex. complex undergoes single-electron oxidation with ferrocenium or AgI salts under mild conditions (5 min temperature) C(sp2)-C(sp2) C(sp2)-NO2 coupling products. Spectroscopic studies implicate formation transient diamagnetic CuIII-σ-aryl intermediate that either (i) second followed by C-C bond-forming reductive elimination (ii) reaction NO2- nucleophile coupling.

Language: Английский

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Diacyl peroxides: practical reagents as aryl and alkyl radical sources

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(55), P. 6707 - 6724

Published: Jan. 1, 2021

This feature article describes the recent achievements in utilizing diacyl peroxides as arylating and alkylating reagents organic synthesis via formation of aryl alkyl radicals.

Language: Английский

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Recent advances in rhodium-catalysed cross-dehydrogenative-coupling between two C(sp²)–H bonds

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(7), P. 1992 - 2012

Published: Jan. 1, 2022

A comprehensive review overviewing the advances in Rh-catalyzed cross-dehydrogenative-coupling period of 2016–2021 is presented.

Language: Английский

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5-Aminopyrazole Dimerization: Cu-Promoted Switchable Synthesis of Pyrazole-Fused Pyridazines and Pyrazines via Direct Coupling of C-H/N-H, C-H/C-H, and N-H/N-H Bonds

Molecules, Journal Year: 2025, Volume and Issue: 30(2), P. 381 - 381

Published: Jan. 17, 2025

A Cu-promoted highly chemoselective dimerization of 5-aminopyrazoles to produce pyrazole-fused pyridazines and pyrazines is reported. The protocol generates switchable products via the direct coupling C-H/N-H, C-H/C-H N-H/N-H bonds, with merits broad substrate scope high functional group compatibility. Gram-scale experiments demonstrated potential applications this reaction. Moreover, preliminary fluorescence results uncovered that dipyrazole-fused may have some in materials chemistry.

Language: Английский

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