Dinuclear Gold‐Catalyzed para‐Selective C−H Arylation of Undirected Arenes by Noncovalent Interactions DOI Open Access
Duanyang Liu, Jie Han, Kai Liu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(44)

Published: Sept. 14, 2023

Abstract The regioselectivity of C−H functionalization is commonly achieved by directing groups, electronic factors, or steric hindrance, which facilitate the identification reaction sites. However, such strategies are less effective for reactants as simple monofluoroarenes due to their relatively low reactivity and modest demands fluorine atom. Herein, we present an undirected gold‐catalyzed para ‐C−H arylation a wide array using air‐stable aryl silanes germanes at room temperature. A high ‐regioselectivity (up 98 : 2) can be realized utilizing dinuclear dppm(AuOTs) 2 (dppm=bis(diphenylphosphino)methane) catalyst hexafluorobenzene solvent. This provides general practical protocol concise construction structurally diverse ‐arylated through activation manner. It features excellent functional group tolerance broad substrate scope (>80 examples). Besides, this strategy also robust other monosubstituted arenes heteroarenes. Our mechanistic studies theoretical calculations suggest that selectivity arises from highly electrophilic flexible Ar−Au(III)−Au(I) species, coupled with noncovalent interaction induced hexafluorobenzene.

Language: Английский

Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings DOI
Jianbin Li, Ding Zhang, Zheng Hu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

Citations

3
Photoinduced copper-catalyzed C–N coupling with trifluoromethylated arenes DOI Creative Commons
Jun Huang, Qi Gao, Zhong Tao

et al.

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

Published: Dec. 14, 2023

Selective defluorinative functionalization of trifluoromethyl group (-CF3) is an attractive synthetic route to the pharmaceutically privileged fluorine-containing moiety. Herein, we report a strategy based on photoexcited copper catalysis activate C-F bond di- or trifluoromethylated arenes for divergent radical C-N coupling with carbazoles and aromatic amines. The use different ligands can tune reaction products diversity. A range substituted, structurally diverse α,α-difluoromethylamines be obtained from via carbazoles, while interesting double ready difluoromethylated arenes. Based this success, carbazole-centered PNP ligand designed optimal ligand, enabling copper-catalyzed construction imidoyl fluorides amines through functionalization. Interestingly, 1,2-difluoroalkylamination styrenes also developed, delivering γ,γ-difluoroalkylamines, bioisostere β-aminoketones, in synthetically useful yields. DFT studies reveal inner-sphere electron transfer mechanism Cu-catalyzed selective activation C(sp3)-F bonds.

Language: Английский

Citations

26
Dinuclear gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes DOI Creative Commons
Cheng‐Long Ji, Hongliang Chen, Qi Gao

et al.

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

Published: May 2, 2024

The enormous and widespread use of organoboronic acids has prompted the development innovative synthetic methodologies to meet demands on structural diversity functional group tolerance. existing photoinduced defunctionalization radical borylation, typically focused conversion one C-X bond (X= Br, I, or other leaving group) into only C-B bond. Herein, we disclose a divergent dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation. A wide range structurally diverse alkyl boronic, α-chloroboronic, gem-diboronic esters can be synthesized in moderate good yields (up 92%). Its robustness is further demonstrated preparative scale applied late-stage diversification complex molecules. process hinges C-Cl relay activation readily available gem-dichloroalkanes through inner-sphere electron transfer, overcoming redox potential limits unreactive chlorides.

Language: Английский

Citations

15
Gold–Manganese Bimetallic Redox Coupling with Light DOI
Siyu Xia, Weipeng Li, Hongliang Chen

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26756 - 26764

Published: Dec. 1, 2023

The classical Au(I)/Au(III) redox couple chemistry has been limited to constructing C–C and C–X bonds, thus, the exploration of elementary reaction gold coupling is very significant enrich its organometallic features. Herein, we report first visible-light-mediated, external oxidant-free using commercially available Mn2(CO)10 generate Mn–Au(III)–Mn intermediates for bimetallic coupling. A wide range structurally diverse heterodinuclear polynuclear L–Au(I)–Mn–L′ complexes (19 examples, up >99% yields) are readily constructed, providing a robust strategy concise construction Au–Mn under mild conditions. mechanistic studies together with DFT calculations support radical oxidative addition •Mn(CO)5 reductive elimination mechanisms from highly active species, representing an important step toward in research. Furthermore, resulting exhibit unique catalytic activity, which divergent nitroarenes can afford azoxybenzenes, azobenzenes, hydrazobenzenes moderate good yields.

Language: Английский

Citations

12
Visible-Light-Induced Regioselective Cascade Radical Cyclization of α-Bromocarbonyls: Access to Benzazepine Derivatives DOI
Nengneng Zhou,

Fangli Zhao,

Lei Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2238 - 2246

Published: Jan. 31, 2024

Visible-light-induced regioselective cascade radical cyclization of α-bromocarbonyls for the synthesis benzazepine derivatives is described. In presence fac-Ir(ppy)3 (2.0 mol %) as a photocatalyst, 2,6-lutidine base, and dichloromethane solvent, reactions proceed smoothly to afford seven-membered rings in good yields. This protocol features broad substrate scope, excellent functional group tolerance, mild reaction conditions. Preliminary mechanistic studies reveal that generation α-carbon more prone react with 1,1-diphenylethylene tethered acrylamide generate stable heterocycle.

Language: Английский

Citations

3
Dinuclear Gold‐Catalyzed para‐Selective C−H Arylation of Undirected Arenes by Noncovalent Interactions DOI Open Access
Duanyang Liu, Jie Han, Kai Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

The regioselectivity of C-H functionalization is commonly achieved by directing groups, electronic factors, or steric hindrance, which facilitate the identification reaction sites. However, such strategies are less effective for reactants as simple monofluoroarenes due to their relatively low reactivity and modest demands fluorine atom. Herein, we present an undirected gold-catalyzed para-C-H arylation a wide array using air-stable aryl silanes germanes at room temperature. A high para-regioselectivity (up 98 : 2) can be realized utilizing dinuclear dppm(AuOTs)2 (dppm=bis(diphenylphosphino)methane) catalyst hexafluorobenzene solvent. This provides general practical protocol concise construction structurally diverse para-arylated through activation manner. It features excellent functional group tolerance broad substrate scope (>80 examples). Besides, this strategy also robust other monosubstituted arenes heteroarenes. Our mechanistic studies theoretical calculations suggest that selectivity arises from highly electrophilic flexible Ar-Au(III)-Au(I) species, coupled with noncovalent interaction induced hexafluorobenzene.

Language: Английский

Citations

8
Trinuclear gold-catalyzed site-selective alkylation of peptides DOI

Qing-Yun Fang,

Chengyihan Gu,

Yinghan Chen

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 14, 2024

Language: Английский

Citations

2
Electrocatalytic conversion of ω-azido carboxylic acids to 1-pyrrolines via a combined process of oxidative decarboxylation and intramolecular Schmidt rearrangement DOI
Kai Yang, Rui Li, Peiming Gu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3391 - 3396

Published: Jan. 1, 2024

An efficient electrochemical oxidation of ω-azido carboxylic acids followed by an intramolecular Schmidt reaction for synthesis 1-pyrroline has been reported.

Language: Английский

Citations

1
Atom-economical synthesis of bicyclo[3.1.0]hexane silanes by gold-catalyzed Si–H bond insertion reaction of 1,6-enynes with hydrosilanes DOI
Guanghui Wang, Haotian Li,

Yong‐Qiang Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(22), P. 5705 - 5709

Published: Jan. 1, 2023

A gold-catalyzed Si–H bond insertion reaction of 1,6-enynes with hydrosilanes via cyclopropyl gold carbene intermediates is herein reported, and a into Ge–H bonds reported for the first time.

Language: Английский

Citations

3
Visible-Light-Enabled Radical Alkynylborylation of Activated Alkenes DOI
Jin Xie, Congjun Zhu,

Shunruo Yao

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 56(11), P. 1711 - 1718

Published: Oct. 31, 2023

Abstract A photoredox-catalyzed protocol for performing radical difunctionalization of alkenes using N-heterocyclic carbene (NHC) boranes and alkynyl bromines is described. The alkynylborylation reaction involves photoredox generation boryl radical, with subsequent addition to the double bond followed by capture bromide form a C–C bond. This method features mild conditions, remarkable chemoselectivity, broad substrate scope good excellent yields (up 89%). modification coumarin derivatives indicates that this approach can provide useful route synthesis complex alkynylborylated products.

Language: Английский

Citations

1