Transition-metal catalyzed C–H activation as a means of synthesizing complex natural products

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(21), P. 7461 - 7503

Published: Jan. 1, 2023

Over the past few decades, advent of C–H activation has led to a rethink among chemists about synthetic strategies employed for multi-step transformations.

Language: Английский

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Isoindolinone Synthesis via One‐Pot Type Transition Metal Catalyzed C−C Bond Forming Reactions

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(17), P. 5344 - 5378

Published: Oct. 30, 2020

Isoindolinone structure is an important privileged scaffold found in a large variety of naturally occurring as well synthetic, biologically and pharmaceutically active compounds. Owing to its crucial role number applications, the synthetic methodologies for accessing this heterocyclic skeleton have received significant attention during past decade. In general, strategies can be divided into two categories: First, direct utilization phthalimides or phthalimidines starting materials synthesis isoindolinones; second, construction lactam and/or aromatic rings by different catalytic methods, including C-H activation, cross-coupling, carbonylation, condensation, addition formal cycloaddition reactions. Especially last mentioned, transition metal catalysts provides access broad range substituted isoindolinones. Herein, recent advances (2010-2020) catalyzed via formation new C-C bonds isoindolinones are reviewed.

Language: Английский

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Rh(III)-Catalyzed [5 + 1] Annulation of Indole-enaminones with Diazo Compounds To Form Highly Functionalized Carbazoles

Organic Letters, Journal Year: 2021, Volume and Issue: 23(11), P. 4406 - 4410

Published: May 21, 2021

A novel Rh(III)-catalyzed C–H activation/annulation cascade of indole-enaminones with diazo compounds was reported to construct diversely functionalized carbazole frameworks. The most notable characteristic is that this transformation could smoothly furnish a [5 + 1] cyclization product good excellent yields (up 95%), accompanied by the thorough removal acetyl and N,N-dimethyl groups two substrates from target products, rather than normally expected [4 2] products.

Language: Английский

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Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp² Carbon Sources for Cp*Rh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(23), P. 14694 - 14701

Published: Nov. 23, 2021

Cp*Rh(III)-catalyzed [4 + 3] annulation of N-methoxy amides for the direct assembly seven-numbered 2H-azepin-2-one frameworks has been realized with gem-difluorocyclopropenes acting as innovative β-monofluorinated three sp2 carbon sources. Either annular arylamides or linear acrylamides embedment various functional groups, including DNA-tagged substrates, were found to be compatible established reaction mode. A redox-neutral Rh(III)–Rh(V)–Rh(III) catalytic cycle, specifically via HOAc-assisted tandem site-/regioselective oxidative addition/reductive elimination/C–F bond cleavage-enabled ring-scission involving unprecedented olefinic C(sp2)–C(sp2) cleavage, deduced based on experimental and computational mechanistic studies. Taken together, our findings not only identified potent efficient coupling partners C–H activation development but also provided a sound basis organic integration transition-metal-catalyzed functionalization cyclopropene fluorine chemistries.

Language: Английский

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Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6881 - 6894

Published: April 14, 2025

Language: Английский

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Regioselective and Chemodivergent Synthesis of Azulenolactones and Azulenolactams from Rhodium(III)‐Catalyzed Reactions of Azulenecarboxamides with Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 363(2), P. 512 - 524

Published: Nov. 4, 2020

Abstract A regioselective and chemodivergent synthetic approach for azulenolactones azulenolactams as a new scaffold was demonstrated through Rh(III)‐catalyzed reaction of N ‐methoxyazulene‐1‐carboxamides with sulfoxonium ylides. Sulfoxonium ylides that act precursor secondary carbene described, leading to the selective formation bearing two substituents on newly introduced double bond. This method functionalization less reactive 2‐position azulene overcome natural reactivity. magnified image

Language: Английский

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Synthesis of Highly Fused Pyrano[2,3-b]pyridines via Rh(III)-Catalyzed C–H Activation and Intramolecular Cascade Annulation under Room Temperature

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(10), P. 6281 - 6294

Published: Feb. 10, 2020

A facile access to the polycyclic-fused pyrano[2,3-b]pyridines has been established under room temperature via Rh(III)-catalyzed C–H bond activation and intramolecular cascade annulation. This strategy features high efficiency, unique versatility, generality it can occur mild conditions in good excellent yields. More importantly, this be extended late-stage functionalization of drugs possessing CN group.

Language: Английский

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Remarkable Ligand Effect on Rh-Catalyzed C–H-Active [3 + 2] Annulation of Ketimines and Alkynes

Organic Letters, Journal Year: 2020, Volume and Issue: 22(12), P. 4903 - 4907

Published: June 3, 2020

Externally added ligands were first found to have a significant impact on the Rh-catalyzed C-H-active [3 + 2] annulation of ketimines and alkynes. Olefin shown remarkable promotion effect for this reaction. The olefin promoted reaction by increasing both turnover rate conversion [Cp*RhCl2]2 in formation rhodacycle C-H activation step.

Language: Английский

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Sulfoximines Assisted Rh(III)-Catalyzed C–H Activation/Annulation Cascade to Synthesize Highly Fused Indeno-1,2-benzothiazines

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(21), P. 15217 - 15227

Published: Oct. 6, 2021

A facile access to highly fused tetracyclic indeno-1,2-benzothiazines has been established via a Rh(III)-catalyzed C-H bond activation and intramolecular annulation cascade between sulfoximides all-carbon diazo indandiones. This strategy is characterized by the fact that coupling partners do not require preactivation, along with its high efficiency, broad substrate generality, transformation. Particularly, conjugated products demonstrate good optical properties can easily enter cells emit bright fluorescence for live cell imaging.

Language: Английский

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Rh-Catalyzed [3+2] Annulation of Cyclic Ketimines and Alkynyl Chloride: A Strategy for Accessing Unsymmetrically Substituted and Highly Functionalizable Indenes

Organic Letters, Journal Year: 2022, Volume and Issue: 24(50), P. 9169 - 9173

Published: Dec. 12, 2022

Alkynyl chlorides were found to be extraordinarily novel electrophiles, which could afford a single regioisomer of the [3+2] annulation adducts with cyclic ketimines by rhodium catalysis. The alkenyl chloride moiety in products provided valuable functional handle for further diverse transformations. Therefore, this research not only synthetic protocol accessing unsymmetrically substituted indenyl amines but also highly divergent solution decorating substituting group postmanipulation chloride.

Language: Английский

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