Rhodium-catalysed decarbonylative C(sp²)–H alkylation of indolines with alkyl carboxylic acids and carboxylic anhydrides under redox-neutral conditions

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(14), P. 2808 - 2812

Published: Jan. 1, 2022

We developed a rhodium-catalysed decarbonylative C(sp2)-H alkylation method for indolines. This reaction facilitates the use of alkyl carboxylic acids and their anhydrides as cheap, abundant non-toxic source under redox-neutral conditions, featuring introduction primary chain, which cannot be addressed by previous radical-mediated decarboxylative reaction. Through mechanistic investigation, we revealed that an initially formed C-7 acylated indoline was transformed into corresponding alkylated via decarbonylation process.

Language: Английский

---

Five-membered ring systems: pyrroles and benzo analogs

Progress in heterocyclic chemistry, Journal Year: 2023, Volume and Issue: unknown, P. 155 - 207

Published: Jan. 1, 2023

Language: Английский

---

Rhodium(III‐Catalyzed C8‐Selective C−H Alkenylation and Alkylation of 1, 2, 3, 4‐Tetrahydroquinolines with Styrenes and Allylic Alcohols

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(7), P. 1027 - 1035

Published: March 16, 2023

Abstract Rh(III)‐catalyzed chelation‐assisted C8‐selective C−H alkenylation and alkylation of 1,2,3,4‐tretrahydroquinolines with styrenes allylic alcohols have been realized. The cationic Rh(III) catalytic system in combination a amount copper acetate uses oxygen as the terminal oxidant catalyzes stereoselective C8‐alkenylation 1,2,3,4‐tetrahydroquinolines to give corresponding products 56–93% yields wide substrate scope broad functional group compatibility. reaction can be scaled up. Moreover, this protocol extended C8‐alkylation alcohols, providing access various 8‐(3‐oxoalkyl)‐1,2,3,4‐tetrahydroquinolines 77–90% yields. selection N‐directing is essential for catalysis, readily installable removable N‐(2‐pyrimidyl) proves optimal choice. Preliminary mechanistic studies are performed gain insights into mechanism. magnified image

Language: Английский

---

Synthesis of α‐Ketoamides via Electrochemical Decarboxylative Acylation of Isocyanides Using α‐Ketoacids as an Acyl Source

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 11(4)

Published: Dec. 20, 2021

Abstract A catalyst‐, transition metal‐, oxidant‐free strategy for the synthesis of α‐ketoamides via an electrochemical decarboxylative acylation isocyanides at room temperature with carbon dioxide as a sole by‐product was developed in this work. This is simple, rapid and practical under mild conditions synthesizing highly functionalized high atom economy.

Language: Английский

---

Dual Palladium-Photoredox-Mediated Regioselective Acylation of Carbazoles and Indolines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(19), P. 13686 - 13698

Published: Sept. 28, 2023

We have described a dual palladium-photoredox-catalyzed highly regioselective acylation of carbazoles and indolines using molecular oxygen as the green oxidant. The reaction shows broad substrate scope good functional group tolerance. Late-stage functionalization carprofen drug derivative, further manipulation products, gram-scale synthesis acylated products were illustrated to show versatility method.

Language: Английский

---

Microwave‐assisted Rhodium(I)‐Catalyzed C8‐Regioselective C−H Alkenylation and Arylation of 1,2,3,4‐Tetrahydroquinolines with Alkenyl and Aryl Carboxylic Acids

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1820 - 1826

Published: Feb. 7, 2024

Abstract Rh(I)‐catalyzed C8‐selective C−H alkenylation and arylation of 1,2,3,4‐tetrahydroquinolines with alkenyl aryl carboxylic acids under microwave assistance have been realized. Using [Rh(CO) 2 (acac)] as the catalyst Piv O acid activator, undergo decarbonylative a wide range acids, affording C8‐alkenylated or arylated 1,2,3,4‐tetrahydroquinolines. This method enables synthesis that would otherwise be difficult to access by means conventional protocols. Moreover, this catalytic system also works well in acids. The activity strongly depends on choice N ‐directing group, readily installable removable ‐(2‐pyrimidyl) group being optimal. pathway is elucidated mechanistic experiments.

Language: Английский

---

Direct Introduction of an Acetyl Group at the α‐Carbon Atom of an Arene Ring through an Amide Photo‐Fries Rearrangement upon Exposure to UV Light

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(26)

Published: April 16, 2024

Abstract We employed an amide photo‐Fries rearrangement for the synthesis benzoheterocyclic compounds and found that direct acylation of α‐carbon atom in arene ring can occur upon exposure to ultraviolet (UV) light. In this reaction, N ‐acetyl group amides underwent α‐position across bridgehead carbon under UV−C The reaction conditions were gentle safe. Moreover, proves be more convenient selectively manipulating comparison traditional approaches involving Lewis acid catalysts or anionic reagents.

Language: Английский

---

Cascade Reaction to Selectively Synthesize Multifunctional Indole Derivatives by Ir^III‐Catalyzed C−H Activation

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(52), P. 13123 - 13127

Published: Aug. 9, 2021

Abstract An effective and condition‐controlled way to synthesize with high selectivity a variety of functionalized indoles potent biological properties has been developed. Notably, 2,4‐dialkynyl indole products were obtained by direct double C−H bond alkynylation, whereas alkynyl at the C4 position could convert carbonyl generate 2‐alkynyl‐3,4‐diacetyl fast effectively. Additionally, one‐pot relay catalytic reaction led 2,5‐di‐alkynyl‐3,4‐diacetyl when using group as directing controlling type quantity additives. A possible mechanism was proposed based on many studies including deuterium‐exchange experiments, necessary conditions product conversion, effect water reaction.

Language: Английский

---

Synthesis of Aryl Nitriles via Aerobic Oxidative Cleavage of Aryl C=C Bonds with (NH4)2CO3 as the Nitrogen Source

Synlett, Journal Year: 2022, Volume and Issue: 33(04), P. 376 - 380

Published: Jan. 18, 2022

Abstract An aerobic oxidative method was developed for conversion of arylethenes to aromatic nitriles using (NH4)2CO3 as the nitrogen source and Cu(NO3)2 catalyst. The present allowed a series underwent cleavage C=C bonds give targeted products in low high yields. In addition, conditions are compatible with many groups such alkyl, alkoxy, N,N-dimethylamino, chloro, bromo, iodo, ester, cyano group, so on.

Language: Английский

---

Palladium‐Catalyzed Direct Alkynylation of Carbazoles with Alkynyl Bromides

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(40)

Published: June 18, 2024

Abstract Carbazole derivatives are vital in medicinal and materials chemistry, yet accessing diverse substitutions remains challenging. Here, we introduce a regioselective approach for C1 C8 alkynylation of carbazoles via palladium‐catalyzed C−H activation. This method provides direct route to mono‐ di‐alkynylated derivatives, addressing the scarcity alkynylated carbazole‐based materials. Our study broadens synthetic toolbox carbazole functionalization, offering potential applications optoelectronics, bio‐imaging, beyond, while contributing developing sustainable activation methodologies.

Language: Английский

---