Rhodium‐Catalyzed Atroposelective Access to Axially Chiral Olefins via C−H Bond Activation and Directing Group Migration

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(1)

Опубликована: Окт. 22, 2021

Axially chiral open-chain olefins represent an underexplored class of platform. In this report, two classes tetrasubstituted axially acyclic have been accessed in excellent enantioselectivity and regioselectivity via C-H activation (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The indoles bearing N-aminocarbonyl afforded C-N acrylamides the assistance racemic zinc carboxylate additive. DFT studies suggest β-nitrogen elimination-reinsertion pathway for migration. Meanwhile, employment N-phenoxycarboxamide delivered C-C enamides migration oxidizing group. Experiments that both cases (hetero)arene substrate adopts well-defined orientation during activation, which turn determines disposition alkyne migratory insertion. Synthetic applications representative are demonstrated.

Язык: Английский

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Synthesis of Naphtho[1′,2′:4,5]furo[3,2-b]pyridinones via Ir(III)-Catalyzed C6/C5 Dual C–H Functionalization of N-Pyridyl-2-pyridones with Diazonaphthalen-2(1H)-ones

Organic Letters, Год журнала: 2024, Номер 26(4), С. 786 - 791

Опубликована: Янв. 22, 2024

Presented herein is an unprecedented synthesis of naphtho[1′,2′:4,5]furo[3,2-b]pyridinones via Ir(III)-catalyzed C6/C5 dual C–H functionalization N-pyridyl-2-pyridones with diazonaphthalen-2(1H)-ones. This protocol forms C–C and C–O bonds in one pot which diazonaphthalen-2(1H)-ones serve as bifunctional reagents, providing both alkyl aryloxy sources. To the best our knowledge, this first example title compounds by using substrates. Notably, method features operational simplicity, good functional group tolerance, high efficiency, atom economy.

Язык: Английский

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Cobalt catalyzed alkenylation/annulation reactions of alkynes via C–H activation: A review

Tetrahedron, Год журнала: 2023, Номер 132, С. 133248 - 133248

Опубликована: Янв. 9, 2023

Язык: Английский

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Chemo-, Regio-, and Stereoselective Assembly of Polysubstituted Furan-2(5H)-ones Enabled by Rh(III)-Catalyzed Domino C–H Alkenylation/Directing Group Migration/Lactonization: A Combined Experimental and Computational Study

ACS Catalysis, Год журнала: 2021, Номер 11(22), С. 13921 - 13934

Опубликована: Ноя. 2, 2021

Exploring multistep cascade reactions triggered by C–H activation are recognized as appealing, yet challenging. Herein, we disclose a Rh(III)-catalyzed domino coupling of N-carbamoyl indoles and 4-hydroxy-2-alkynoates for the streamlined assembly highly functionalized furan-2(5H)-ones in which carbamoyl-directing group (DG) is given dual role an auxiliary migrating acylating reagent via cleavage stable C–N bonds at room temperature. More importantly, obtained furan-2(5H)-one skeleton could be further under air situ C5–H hydroxylation simply switching solvent or additive, providing fully substituted with installation alcohol-based C5 quaternary carbon center. Detailed experimental studies density functional theory calculations reveal that Rh(III)-mediated tandem activation/alkyne insertion/DG migration/lactonization accounts developed transformation to achieve high functionalities observed exclusive selectivity. The potential biological application class potent PPARγ ligands highlights synthetic utility methodology. This protocol endowed several salient features including efficient activation, excellent chemo-, regio-, stereoselectivity, bond-forming efficiency (e.g., two C–C C–O bonds), solvent- additive-controlled product selectivity, good functional-group compatibility, mild redox-neutral conditions.

Язык: Английский

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Iron-Catalyzed Regio- and Stereoselective C–H Alkenylation of Pivalophenone Derivatives with Unsymmetric Internal Alkynes

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(3), С. 1890 - 1897

Опубликована: Янв. 13, 2023

Here we report an ortho-C-H alkenylation of aromatic ketones with unsymmetric internal alkynes catalyzed by iron phosphine complex, Fe(PMe3)4. The use a catalytic amount PtBu3 as additive was found to improve the product yields. proceeds regio- and stereoselectively give corresponding styrene derivatives.

Язык: Английский

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New thiazole, thiophene and 2-pyridone compounds incorporating dimethylaniline moiety: synthesis, cytotoxicity, ADME and molecular docking studies

BMC Chemistry, Год журнала: 2024, Номер 18(1)

Опубликована: Март 14, 2024

Abstract Various sets of thiazole, thiophene, and 2-pyridone ring structures containing a dimethylaniline component were synthesized. Substituted thiazoles 2 – 3 thiophenes 5 7 produced by reacting thiocarbamoyl compound 4 with α-halogenated reagents in different basic conditions. Also, series derivatives 9a f substituted was synthesized through Michael addition malononitrile to α,β-unsaturated nitrile 8a . The products structurally proven spectroscopic methods such as IR, 1 H NMR, 13 C MS data. Furthermore, the anti-cancer efficacy compounds assessed using MTT assay on two cell lines: hepatocellular carcinoma ( HepG-2 ) breast cancer MDA-MB-231 ). results showed highest growth inhibition for , 6 9c which further examined their IC 50 values. equipotent activity (IC = 1.2 µM) against line compared Doxorubicin 1.1 µM). Compounds very good ADME assessments drug administration. Moreover, PASS theoretical prediction high antimitotic antineoplastic activities well potent insulysin enzyme (IDE). Molecular docking stimulations performed CDK1/CyclinB1/CKS2 (PDB ID: 4y72) BPTI 2ra3). When docked into 4y72), all tested considerable inhibition, derivative 9d had maximum binding affinity (− 8.1223 kcal/mol). While thiophene offered 7.5094 kcal/mol) when Graphical

Язык: Английский

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Recent Advances in the High‐Valent Cobalt‐Catalyzed C−H Functionalization of N‐Heterocycles

The Chemical Record, Год журнала: 2021, Номер 22(3)

Опубликована: Дек. 21, 2021

Abstract Direct functionalization of heterocycles using C−H activation widely relies on the precious metal complexes. In past decade, use earth abundant and inexpensive transition to functionalize has become an attractive alternate strategy. This concept is also interesting due unique reactivity pattern these metals. this context we other research groups have utilized high‐valent cobalt complexes as readily available catalyst for heterocycles. review, intend brief recent progress made in area catalyzed N ‐containing

Язык: Английский

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Switching the Reactivity of the Nickel-Catalyzed Reaction of 2-Pyridones with Alkynes: Easy Access to Polyaryl/Polyalkyl Quinolinones

Organic Letters, Год журнала: 2022, Номер 24(33), С. 6122 - 6127

Опубликована: Авг. 11, 2022

A Ni-catalyzed C6 followed by C5 cascade C-H activation/[2 + 2 2] annulation of 2-pyridone with alkynes has been achieved. change in the reaction pathway was achieved tuning conditions and incorporating a directing group. wide variety substrates are amenable to this transformation. The key success for transformation is use sodium iodide as an additive. More importantly, we detected five-membered metallacycle intermediate through HRMS wherein ligated metal.

Язык: Английский

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Rh(III)-Catalyzed Weakly Coordinating 2-Pyridone-Directed Oxidative Annulation Using Internal Alkynes: A Reversal in Selectivity

Organic Letters, Год журнала: 2022, Номер 24(46), С. 8470 - 8475

Опубликована: Ноя. 14, 2022

A rhodium(III)-catalyzed Satoh-Miura type oxidative annulation of N-aryl 2-pyridone derivatives is described using internal alkyne as a coupling partner. weakly coordinating carbonyl group the ring utilized for this transformation. The reaction proceeds with broad scope and wide functional tolerance. solvent plays an important role in developed method to furnish different class annulated product. preliminary investigation was carried out explore photophysical properties obtained polyarylated N-naphthyl 2-pyridones.

Язык: Английский

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Pd(II)-Catalyzed Oxidative Naphthylation of 2-Pyridone through N–H/C–H Activation Using Diarylacetylene as an Uncommon Arylating Agent

Organic Letters, Год журнала: 2023, Номер 25(11), С. 1952 - 1957

Опубликована: Март 10, 2023

A Pd(II)-catalyzed straightforward oxidative naphthylation of unmasked 2-pyridone derivatives is described using a twofold internal alkyne as coupling partner. The reaction proceeds through N–H/C–H activation to provide polyarylated N-naphthyl 2-pyridones. An unusual annulation at the arene C–H bond diarylalkyne leads formation 2-pyridones, where 2-pyridone-attached phenyl ring naphthyl polyaryl-substituted. Mechanistic studies and DFT calculations suggest plausible mechanism based on activation. were studied explore encouraging photophysical properties.

Язык: Английский

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