Iridium(III)-Catalyzed Intermolecular Mild N-Arylation of Aliphatic Amides Using Quinoid Carbene: A Migratory Insertion-Based Approach

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(17), P. 10847 - 10854

Published: Aug. 17, 2021

An efficient Ir(III)-catalyzed straightforward intermolecular N-arylation of acyclic aliphatic amides has been achieved using quinone diazide as a coupling partner. The reaction developed under simple and mild conditions with broad substrate scope. bidentate picolinamide group is essential for successful transformation. Mechanistic studies DFT calculations highlighted the migratory insertion-based pathway. method exhibits different reactivities compared to reactions related diazo/azide congeners Rh(III)/Ir(III) catalysis.

Language: Английский

---

Ru(II)-Catalyzed C–H Functionalization of 2-Arylbenzimidazoles with Iodonium Ylides: A Straightforward Access to Bridgehead Polycyclic N-Heterocycles

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(21), P. 13757 - 13762

Published: Oct. 25, 2022

Herein, we disclose an efficient ruthenium-catalyzed C–H functionalization of 2-arylbenzimidazoles/2-arylimidazoles with iodonium ylides leading to substituted tetracyclic and pentacyclic bridgehead N-heterocycles, wherein ylide acts as a carbene precursor. For the first time, proceeds through Ru–carbenoid intermediate. Further, synthetic utility this protocol was successfully shown for gram-scale synthesis useful transformations.

Language: Английский

---

α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C–H activation: a safe carbene precursor and a weak directing group

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(5), P. 879 - 909

Published: Dec. 6, 2022

Transition metal-catalyzed cross-coupling of sp2 C-H bonds with diazo compounds via carbene migratory insertion represents an efficient strategy for the construction C-C and C-heteroatom in organic synthesis. Despite popularity as coupling partners activation, they pose serious safety stability issues due to potential exothermic reactions linked release N2 gas. However, compared compounds, sulfoxonium ylides are generally crystalline solids, more stable, widely used industrial scales, easier/safer prepare. Therefore, recent years have witnessed upsurge employing α-carbonyl alternative surrogate transition activation. Unlike contain inherent serve a partner well weak directing group. This review will summarize progress made both categories reactions.

Language: Английский

---

Palladium-Catalyzed Migratory Insertion of Carbenes and C–C Cleavage of Cycloalkanecarboxamides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(2), P. 536 - 541

Published: Jan. 4, 2022

A palladium catalyzed reaction of cycloalkanecarboxamides and diazomalonates or bis(phenylsulfonyl)diazomethane has been developed. The proceeds via carbene migratory insertion cascade C-C cleavage pathways. Cycloalkanecarboxamides with four to seven membered rings are applicable in the transformation. series ring opening products were prepared moderate yields. finding provides valuable clues for development new reactions involving unstrained C(sp3)-C(sp3) bonds.

Language: Английский

---

Catalyst- and additive-free syntheses of rhodanine andS-alkyl dithiocarbamate derivatives from sulfoxonium ylides

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(11), P. 1509 - 1512

Published: Jan. 1, 2023

An efficient catalyst- and additive-free facile access to rhodanine S -alkyl dithiocarbamate derivatives via multi-component reaction of amines, CS 2 α-ester sulfoxonium ylides in methanol has been described.

Language: Английский

---