Visible-Light-Mediated Ruthenium-Catalyzed para-Selective Alkylation of Unprotected Anilines DOI
Xinyan Lv,

Yaohang Cheng,

Yingxiao Zong

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(11), С. 7310 - 7321

Опубликована: Май 15, 2023

Anilines are important moieties in organic chemistry, pharmaceuticals, and materials science. Although para-selective functionalization of anilides tertiary anilines is well established, unprotected have posed a challenge. Herein, we report visible-light-mediated Ru(II)-catalyzed para-alkylation anilines. The distinct Ru(II)–aniline complex enabled the reaction to proceed with extremely high efficiency (2 h) under mild conditions. good functional group tolerance allowed late-stage even aggregation-induced emission luminogen labeling natural products drugs. A mechanistic investigation suggests that crucial for both triggering controlling para-selectivity.

Язык: Английский

Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules DOI Creative Commons
Jamie H. Docherty,

Thomas M. Lister,

Gillian McArthur

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(12), С. 7692 - 7760

Опубликована: Май 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Язык: Английский

Процитировано

241

One-Shot Construction of BN-Embedded Heptadecacene Framework Exhibiting Ultra-narrowband Green Thermally Activated Delayed Fluorescence DOI
Yusuke Sano,

Toshiki Shintani,

Masahiro Hayakawa

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11504 - 11511

Опубликована: Май 16, 2023

BN-embedded nonacene, tridecacene, and heptadecacene frameworks were constructed using one-shot quadruple, sextuple, octuple borylation reactions, respectively. The key to success is the judicious choice of borylating reagents long-chain alkyl-substituted carbazolyl groups as boron-trapping groups, which suppressed decrease in HOMO energy insolubilization associated with borylation. Based on product yields, each electrophilic C-H proceeded >99% yield, best efficiency reported so far for reactions. Owing multiple resonance effects boron nitrogen, prepared acenes exhibited ultra-narrowband green thermally activated delayed fluorescence full-width at half-maximum 12-16 nm; moreover, their kRISC values order 105 s-1. We fabricated an organic light-emitting diode by employing nonacene emitter, high external quantum (EQE) 28.7%. device also showed a minimum roll-off EQE 25.8% 1000 cd m-2.

Язык: Английский

Процитировано

74

Transition metal–catalyzed remote C─H borylation: An emerging synthetic tool DOI Creative Commons
Mirja Md Mahamudul Hassan, Saikat Guria, Sayan Dey

и другие.

Science Advances, Год журнала: 2023, Номер 9(16)

Опубликована: Апрель 21, 2023

Transition metal–catalyzed C─H bond activation and borylation is a powerful synthetic method that offers versatile transformation from organoboron compounds to virtually all other functional groups. Compared the ortho-borylation, remote remains more challenging owing inaccessibility of these bonds. Enforcing metal catalyst toward bonds needs well-judged design through proper ligand development. This review article aims summarize recent discoveries for by employment new catalyst/ligand with help steric ligand, noncovalent interactions. It has been found now takes part in total synthesis natural products shorter route. Whereas, Ir-catalyzed predominant, cobalt also started affect this field sustainable cost-effective

Язык: Английский

Процитировано

66

Photoelectrochemically driven iron-catalysed C(sp3)−H borylation of alkanes DOI

Yangmin Cao,

Cheng Huang, Qingquan Lu

и другие.

Nature Synthesis, Год журнала: 2024, Номер 3(4), С. 537 - 544

Опубликована: Янв. 31, 2024

Язык: Английский

Процитировано

23

Copper-Mediated Dehydrogenative C(sp3)–H Borylation of Alkanes DOI Creative Commons
Ruocheng Sang, Wangyujing Han, Hanwen Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15207 - 15217

Опубликована: Июль 6, 2023

Borylations of inert carbon-hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated involving hydrogen atom transfer pathways have emerged as attractive alternatives because they provide complimentary regioselectivities and proceed metal-free However, net oxidative processes require stoichiometric oxidants therefore cannot compete the high economy their precious-metal-catalyzed counterparts. Herein, we report that CuCl2 catalyzes radical-mediated, C(sp3)-H alkanes bis(catecholato)diboron This is a result an unexpected dual role copper catalyst, promotes oxidation reagent to generate electrophilic bis-boryloxide acts effective borylating agent in subsequent redox-neutral photocatalytic C-H borylations.

Язык: Английский

Процитировано

40

Dual-Ligand Catalyst for the Nondirected C–H Olefination of Heteroarenes DOI
Guangrong Meng, Zhen Wang, Hau Sun Sam Chan

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8198 - 8208

Опубликована: Март 28, 2023

Pd(II)-catalyzed nondirected C-H functionalization of heteroarenes is a significant challenge for the following reasons: poor reactivity electron-deficient heterocycles and unproductive coordination Lewis basic nitrogen atoms. Existing methodologies using palladium catalysis often employ large excess heterocycle substrates to overcome these hurdles. Despite recent advances in arenes that allow them be used as limiting reagents, reaction conditions are incompatible with heteroarenes. Herein we report dual-ligand catalyst enables olefination without substrate. In general, use 1-2 equiv was sufficient obtain synthetically useful yields. The rationalized by synergy between two types ligands: bidentate pyridine-pyridone ligand promotes cleavage; monodentate substrate acts second form cationic Pd(II) complex has high affinity arenes. proposed cooperation supported combination X-ray, kinetics, control experiments.

Язык: Английский

Процитировано

35

Simple Ether‐Directed Enantioselective C(sp3)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis DOI Open Access
Tian Xie, Lili Chen, Zhenlu Shen

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 10, 2023

Reported here is an efficient and simple ether-directed iridium-catalyzed enantioselective C(sp3 )-H borylation of cyclopropanes. Various functional groups were well-tolerated, affording a vast array chiral cyclopropanes with high enantioselectivities. We also demonstrated that the turnover numbers current reaction could be up to 335.

Язык: Английский

Процитировано

28

Selective Methane Oxidation by Heterogenized Iridium Catalysts DOI
Haoyi Li,

Muchun Fei,

Jennifer L. Troiano

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(2), С. 769 - 773

Опубликована: Янв. 3, 2023

Oxidative methane (CH4) carbonylation promises a direct route to the synthesis of value-added oxygenates such as acetic acid (CH3COOH). Here, we report strategy realize oxidative CH4 through immobilized Ir complexes on an oxide support. Our immobilization approach not only enables activation but also allows for easy separation and reutilization catalyst. Furthermore, show that key step, methyl migration, forms C–C bond, is sensitive electrophilicity carbonyl, which can be tuned by gentle reduction centers. While as-prepared catalyst mainly featured Ir(IV) preferred CH3COOH production, reduced featuring predominantly Ir(III) led significant increase CH3OH production at expense yield CH3COOH.

Язык: Английский

Процитировано

26

Noncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation DOI Creative Commons
Yushu Jin,

Ramadoss Boobalan,

Sobi Asako

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 17, 2024

Abstract Exploitation of noncovalent interactions for recognition an organic substrate has received much attention the design metal catalysts in synthesis. The CH–π interaction is especially interest molecular because both C–H bonds and π electrons are fundamental properties molecules. However, their weak nature, these have been less utilized control reactions. We show here that can be used to kinetically accelerate catalytic activation arenes by directly recognizing π-electrons arene substrates with a spirobipyridine ligand. Computation ligand kinetic isotope effect study provide evidence between backbone substrate. rational exploitation will open new avenues catalysis.

Язык: Английский

Процитировано

10

Photocatalytic Direct Borylation of Benzothiazole Heterocycles via a Triplet Activation Strategy DOI

Ze‐Le Chen,

Claire Empel, Yang Xie

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 11, 2025

Boron compounds are widely employed in organic chemistry, pharmaceuticals, and materials science. Among them, borylated heterocycles serve as versatile synthons for the construction of new C-C or C-heteroatom bonds via coupling radical processes. Such methods direct C-H borylation reactions high synthetic value to reduce number steps amount waste improve efficiency. Despite significant advances, remains an ongoing challenge with great potential applications chemical synthesis. Herein, we describe a photocatalytic reaction five-membered ring by employing stable N-heterocyclic carbene borane borylating reagent photoredox catalyst. Under green mild conditions, was achieved on series benzo-fused heterocyclic compounds. Further studies demonstrate utility this approach pharmaceutical agrochemical research.

Язык: Английский

Процитировано

2