Palladium-Catalyzed Allylic C–H Oxidative Annulation for Assembly of Functionalized 2-Substituted Quinoline Derivatives

Li, Chunsheng; Li, Jianxiao; An, Yanni; Peng, Jianwen; Wu, Wanqing; Jiang, Huanfeng

doi:10.1021/acs.joc.6b01909

Cited by 52 publications

(23 citation statements)

References 72 publications

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“…According to TP3 , the reaction of quinoline N -oxide (145 mg, 1 mmol) with a di(3-cyanophenyl) zinc reagent (7.9 mL, 0.19 M) afforded the desired product 43 as a white solid (79 mg, 34%): 1 H NMR (400 MHz, CDCl 3 ) δ 8.51 (t, J = 1.7 Hz, 1H), 8.40 (dt, J = 8.0, 1.5 Hz, 1H), 8.28 (d, J = 8.6 Hz, 1H), 8.17 (d, J = 8.3 Hz, 1H), 7.86 (d, J = 8.6 Hz, 2H), 7.79–7.71 (m, 2H), 7.63 (t, J = 7.8 Hz, 1H), 7.57 (ddd, J = 8.1, 6.8, 1.2 Hz, 1H); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 154.6, 148.2, 140.7, 137.4, 132.5, 131.6, 131.3, 130.2, 129.8, 129.6, 127.5, 127.5, 127.0, 118.8, 118.3, 113.1. All the resonances in the 1 H and 13 C NMR spectra were consistent with the reported values …”

Section: Methodssupporting

confidence: 89%

Direct C–H Arylation and Alkylation of Electron-Deficient Heteroaromatic Compounds with Organozinc Reagents

Peng

Wang

et al. 2021

Organometallics

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A direct and convenient method for the C−H arylation and alkylation of electron-deficient N-heteroarenes with readily available organozinc reagents has been developed. This transformation could be readily performed in the absence of a transition-metal catalyst and external oxidants, affording a wide range of substituted heteroarenes with good functional group tolerance in good to excellent yields. The developed simple protocol is scalable to the gram level and suitable for late-stage modification of bioactive molecules and drugs.

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Section: Methodssupporting

confidence: 89%

Direct C–H Arylation and Alkylation of Electron-Deficient Heteroaromatic Compounds with Organozinc Reagents

Peng

Wang

et al. 2021

Organometallics

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“…Focusing on high efficiency and atom economy, Wu and Jiang developed conditions in DMSO media using a Pd(II) catalyst, TsOH, water and molecular oxygen as a terminal oxidant to achieve a wide scope of quinolines products from a variety of allyl benzenes and anilines with moderate to excellent yields (Scheme 42). 72 The reaction mechanism goes through the coordination of allylic bond to the Pd(II) species, which allows the water attack and form the enol, that is rapidly oxidized by molecular oxygen. After an imine formation through cinnamaldehyde and aniline, a conjugate addition takes place, when another molecule of aniline mediated by acid finds the imine, converting it into a labile diazetidinium cation, and thus giving the desired product due to the occurrence of irreversible cyclization/elimination steps.…”

Section: Aerobic Dehydrogenative Coupling/functionalizationmentioning

confidence: 99%

“…Focusing on high efficiency and atom economy, Wu and Jiang developed conditions using a Pd(II) catalyst, TsOH, water, DMSO and molecular oxygen as a terminal oxidant to prepare a wide range of quinoline products in moderate to excellent yields from different allyl benzenes and anilines (Scheme 42 ). 72 The reaction mechanism proceeds via coordination of the allylic bond to the Pd(II) species, which allows attack of water to form an enol, which is rapidly oxidized by molecular oxygen. After imine formation between cinnamaldehyde and the aniline, a conjugate addition takes place during which another molecule of the aniline, mediated by acid, reacts with the imine converting it into a labile diazetidinium cation.…”

Section: Aerobic Dehydrogenative Coupling/functionalizationmentioning

confidence: 99%

Recent Advances in Palladium-Catalyzed Oxidative Couplings in the Synthesis/Functionalization of Cyclic Scaffolds Using Molecular Oxygen as the Sole Oxidant

Barboza¹,

Dantas²,

Costa³

et al. 2021

Synthesis

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Over the past years, Pd(II)-catalyzed oxidative couplings enabled the achievement of molecular scaffolds with high structural diversity via C−C, C-N and C-O bond-formation reactions. In contrast to the use of stoichiometric amounts of more common oxidants, such as metal salts (Cu and Ag) and benzoquinone derivatives, the use of molecular oxygen in the direct or indirect regeneration of Pd(II) species presents itself as a more viable alternative in terms of economy and sustainability. In this review, we describe recent advances on the development Pd-catalyzed oxidative cyclizations/functionalizations, where molecular oxygen plays a pivotal role as the sole stoichiometric oxidant. 1 Introduction 2 Oxidative C-C and C-Nu Coupling 2.1 Intramolecular Oxidative C-Nu Heterocyclization Reactions 2.1.1 C-H Activation 2.1.2 Wacker/aza-Wacker Type Cyclization 2.1.3 Tandem Wacker/aza-Wacker and Cyclization/Cross Coupling Reactions 2.2 Intermolecular Oxidative C-Nu Heterocoupling Reactions 2.3 Intramolecular Oxidative (C-C) Carbocyclization Reactions 2.4 Intermolecular Oxidative C-C Coupling Reactions 2.4.1 Cyclization Reactions 2.4.2 Cross-Coupling Reactions 2.4.3 Homo-Coupling Reactions 3 Aerobic Dehydrogenative Coupling/Functionalization 4 Oxidative C-H Functionalization 5 Summary

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“…Since 2014, we have also successively developed as eries of aerobico xidative allylic CÀHf unctionalizations of alkenes, withO 2 as the sole oxidant participating in the cycle (Scheme 28). Many different kinds of allylic polyfluoroarene derivatives, [46] allylic azides, [47] a,b-unsaturated esters, [48] quinoline derivatives, [49] a,b-unsaturated aldehydes, and allylic alcohols [50] were appliedi nt his system.…”

Section: Atmospheric O 2 As the Sole Oxidantmentioning

confidence: 99%

Palladium‐Catalyzed Oxidation Reactions of Alkenes with Green Oxidants

Jiang

2019

ChemSusChem

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Transition‐metal‐catalyzed oxidative functionalization of alkenes has emerged as a powerful and valuable tool in modern organic synthesis. Recently, many methods have been established for the assembly of C−C and C–heteroatom bonds, which provides tremendous possibility for application in biology, medicine, and materials science. However, the use of stoichiometric amounts of strong oxidants leads to poor selectivity, low atom economy, and a series of undesired waste products. By contrast, green oxidants, such as O2, H2O2, or tert‐butyl hydroperoxide (TBHP), have bright prospects due to their attributes of mild, low cost, and great sustainability in transition‐metal‐catalyzed oxidation reactions. Based on the great and unique potential for the development of aerobic reactions, this review mainly highlights homogenous palladium‐catalyzed green oxidations of alkenes that have been reported in recent years. These methods provide new strategies for the transformation and functionalization of alkenes; some of them have also been successfully applied to the synthesis of the core structures of drugs and natural products. Additionally, through in‐depth studies of the reaction mechanisms in this field, it is believed that palladium‐catalyzed green oxidation reactions of alkenes with O2, H2O2, or TBHP will create added value for organic synthetic chemistry.

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Palladium-Catalyzed Allylic C–H Oxidative Annulation for Assembly of Functionalized 2-Substituted Quinoline Derivatives

Cited by 52 publications

References 72 publications

Direct C–H Arylation and Alkylation of Electron-Deficient Heteroaromatic Compounds with Organozinc Reagents

Direct C–H Arylation and Alkylation of Electron-Deficient Heteroaromatic Compounds with Organozinc Reagents

Recent Advances in Palladium-Catalyzed Oxidative Couplings in the Synthesis/Functionalization of Cyclic Scaffolds Using Molecular Oxygen as the Sole Oxidant

Palladium‐Catalyzed Oxidation Reactions of Alkenes with Green Oxidants

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