Ni-catalyzed benzylic β-C(sp3)–H bond activation of formamides DOI Creative Commons
Rong-Hua Wang, W. Xu, Hongli Wu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 22, 2022

The development of transition metal-catalyzed β-C-H bond activation via highly-strained 4-membered metallacycles has been a formidable task. So far, only scarce examples have reported to undergo metallacycles, and all them rely on precious metals. In contrast, earth-abundant inexpensive 3d still remains an elusive challenge. Herein, we report phosphine oxide-ligated Ni-Al bimetallic catalyst activate secondary benzylic C(sp3)-H bonds formamides nickelacycles, providing series α,β-unsaturated γ-lactams in up 97% yield.

Language: Английский

Deciphering the Mechanistic Insights of Temporary Directing-Group-Assisted meta-Alkenylation of Complex Biaryl Systems DOI
Nupur Goswami, Nikunj Kumar, Sukdev Bag

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 11091 - 11103

Published: Aug. 7, 2023

The recently developed palladium-catalyzed C(sp2)–H olefination of 2-arylbenzaldehyde with the aid a temporary directing group (TDG) via reversible imine formation delivers selective meta-C–H functionalization and possesses significant advantages over well-established covalently attached (DG) approach. In this report, combined computational experimental investigation has been performed to elucidate detailed reaction mechanism origins such remote meta-selectivity. proceeds in three major steps: C–H activation, 1,2-migratory insertion, β-hydride elimination. While insertion olefin is found be turnover-determining step, selectivity predetermined by preceding activation step. observations have corroborated along experimentally conducted order determination studies, primary kinetic isotope effect (PKIE) study, free energy correlation Hammett plots. A DG-bound Pd complex shown competent promote meta-alkenylation. All possible Pd-catalyzed template-directed (ortho′, ortho, meta, para) olefinations 2-aryl benzaldehyde/aniline computationally investigated. density functional theory (DFT)-based computations indicated that other reactions necessitate higher barriers compared meta-olefination. Distortion-interaction analysis (DIA), noncovalent interaction (NCI) analysis, isodesmic studies were executed unravel mystery behind origin meta-regioselectivity.

Language: Английский

Citations

9
Pd(ii)-catalyzed meta-C–H bromination and chlorination of aniline and benzoic acid derivatives DOI Creative Commons
Hao Wang, Lei Fu,

Chunlin Zhou

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(29), P. 8686 - 8692

Published: Jan. 1, 2022

The classic electrophilic bromination leads to

Language: Английский

Citations

15
Asymmetric Remote meta-C–H Activation Controlled by a Chiral Ligand DOI
Hang Wang, Huiling Li,

Xiahe Chen

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(21), P. 13435 - 13445

Published: Oct. 19, 2022

The use of a chiral ligand for stereocontrol has assisted the development number asymmetric functionalization proximal C–H bonds. Herein, we report ligand-controlled, remote meta-C–H activation arenes, leading to olefination and arylation hydrocinnamic acid derivatives through desymmetrization with Ac-L-Phe-OH as using Pd(II) catalyst. origins enantioselectivity were explained density functional theory calculations. larger distortion energy substrate part in bond transition structure S-TS1 is major controlling factor that disfavors formation S-enantiomer product.

Language: Английский

Citations

14
Iridium(iii)-catalyzed β-trifluoromethyl enone carbonyl-directed regioselective ortho-C(sp2)–H olefination DOI
Haritha Sindhe,

Akshay Kamble,

Malladi Mounika Reddy

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(6), P. 1162 - 1166

Published: Jan. 1, 2024

Herein, we have reported iridium( iii )-catalyzed β-trifluoromethyl enone carbonyl-directed regioselective aromatic ortho -C(sp 2 )–H olefination with acrylates under oxidative conditions to access diverse -olefinated β-CF 3 enones.

Language: Английский

Citations

2
Repurposing a supramolecular iridium catalyst via secondary Zn⋯OC weak interactions between the ligand and substrate leads to ortho-selective C(sp2)–H borylation of benzamides with unusual kinetics DOI Creative Commons
Jonathan Trouvé,

Vanessa Delahaye,

Michele Tomasini

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 11794 - 11806

Published: Jan. 1, 2024

Supramolecular catalysts based on a zinc-porphyrin molecular recognition site and catalytically active iridium enabled the selective ortho -C–H borylation of benzamides under regime in which C–H activation step is not rate-determining.

Language: Английский

Citations

2
Ligand-Controlled Nondirected meta- or para-C–H Olefination of Silyl-Protected Phenols DOI
Guangrong Meng, Jie-Lun Yan, Nikita Chekshin

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 12806 - 12813

Published: Aug. 9, 2024

Recent advances in ligand design have enabled Pd(II)-catalyzed nondirected C–H functionalization using arenes as the limiting reagent, but achieving catalyst control over site selectivity these transformations remains a significant challenge. Instead, is typically governed by inherent steric and electronic properties of arene substrates or directing effects. Consequently, it can be difficult to selectively functionalize para-position electron-deficient meta-positions electron-rich arenes, respectively. In this report, we demonstrate that choice olefination switch between activated para- deactivated meta-C–H bonds silyl-protected phenols, thereby highly enabling site-selective either position with broad substrate scopes. Specifically, monodentate 2-pyridone ligands enable high-yielding conventional para-selectivity largely intrinsic bias substrate, whereas dual-ligand system consisting bidentate pyridine–pyridone pyridine reversed site-selectivity favor relatively meta-position. Mechanistic studies indicate renders para-C–H palladation reversible not palladation, favoring arenes.

Language: Английский

Citations

2
Formal C–H/C–I Metathesis: Site-Selective C–H Iodination of Anilines Using Aryl Iodides DOI
Ning Wang,

Zhuomin Chi,

Xinchao Wang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(20), P. 3657 - 3662

Published: May 16, 2022

Functional group metathesis has the potential to render mild reaction conditions for C-H functionalization. Protocols meta- and ortho-C-H iodination of aniline derivatives via formal C(sp2)-H/C(sp2)-I using 2-nitrophenyl iodides as iodinating reagents are reported herein. These protocols led production a range valuable iodinated derivatives. results demonstrate developing novel site-selective activation reactions with electron-rich compounds, since can often been utilized in functional reactions.

Language: Английский

Citations

10
Meta-Selective C–H Functionalization of Arylsilanes Using a Silicon Tethered Directing Group DOI

Jaehan Bang,

Seyun Gi,

Yoonjung Lee

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(28), P. 5181 - 5185

Published: July 13, 2022

We describe meta-selective C-H functionalization of arylsilanes using a Si-tethered directing group. The current method enables selective alkenylation arenes bearing variety functional groups, and several electron-deficient olefins are also applicable as coupling partners. Further group transformations the silicon-tethered provide multisubstituted efficiently.

Language: Английский

Citations

10
Macrocyclization via remote meta-selective C–H olefination using a practical indolyl template DOI Creative Commons
Pengfei Zhang, Zhiwei Jiang, Zhoulong Fan

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(31), P. 8279 - 8287

Published: Jan. 1, 2023

Macrocyclization via palladium-catalyzed intramolecular meta -selective C–H olefination was achieved through utilizing a readily accessible and cleavable indolyl template.

Language: Английский

Citations

5
Access to distal meta-C–H functionalization of arylmethanesulfonic acid derivatives DOI

Dasari Srinivas,

Kurella Mounika,

Gedu Satyanarayana

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(59), P. 9106 - 9109

Published: Jan. 1, 2023

Herein, we report the meta-C-H olefination of arylmethanesulfonates aided by a potentially versatile aliphatic nitrile-directing group under microwave irradiation conditions with fair to very good yields and outstanding regioselectivities. Significantly, protocol showed broad substrate scope including olefin-derived drugs cyclic olefins. Remarkably, dual bond was amenable generating bis-olefination products.

Language: Английский

Citations

4