Palladium-catalyzed carbene coupling of <i>N</i>-tosylhydrazones and arylbromides to synthesize cross-conjugated polymers

Zhou, Qi; Gao, Yunpeng; Xiao, Yiyang; Yu, Lefei; Fu, Zihao; Li, Zi‐Chen; Wang, Jianbo

doi:10.1039/c8py01529e

Cited by 23 publications

(10 citation statements)

References 48 publications

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“…Due to its advantageous functional group tolerance, this cross-coupling reaction has vast potential in synthetic chemistry, and proven applications in cancer treatments, 233 natural product synthesis, 234,235 and polymer synthesis. 236 Based on the fact that N -tosylhydrazones exhibit nucleophilic behaviour, in combination with previous palladium studies, Barluenga and coworkers 227 proposed the mechanism to begin with oxidative addition of the organic halide to the active palladium(0) complex (Figure 5.1). The N -tosylhydrazone undergoes base-mediated decomposition, and the product then binds to the palladium complex, resulting in a palladium-carbene complex.…”

Section: Introductionmentioning

confidence: 96%

A mechanistic investigation of the Pd-catalyzed cross-coupling betweenN-tosylhydrazones and aryl halides

2021

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Section: Introductionmentioning

confidence: 96%

A mechanistic investigation of the Pd-catalyzed cross-coupling betweenN-tosylhydrazones and aryl halides

2021

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“…In 2015, Gu and co-workers reported an asymmetric version of this reaction, in which axially chiral vinyl arenes were obtained in high enantioselectivity (Scheme d) . Recently, our group successfully applied this type of coupling reactions in polymerization . A type of cross-conjugated polymers, namely poly(arylene-1,1-vinylidene)s (iso-PAVs), can be obtained through either AB-type or A 2 +B 2 -type polymerization (Scheme e).…”

Section: Ketones As Alkenyl Coupling Partnersmentioning

confidence: 99%

Transition-Metal-Catalyzed Cross-Coupling with Ketones or Aldehydes via N-Tosylhydrazones

2020

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Ketones and aldehydes play central roles in organic synthesis. There are numerous broadly used reactions that are related to the carbonyl reactivity, such as Grignard reactions, Wittig reactions, aldol reactions, and so on. In addition, the formation of enol triflates is a classic protocol that enables the ketones to be applied in transition-metal-catalyzed cross-coupling reactions, in which case the ketones are considered as the precursors of alkenyl electrophiles in the C−C bond-forming transformations. In the past decade, a new type of ketone-or aldehyde-based C−C bond-forming transformations has emerged. In this type of reactions, the ketones or aldehydes are first converted to their corresponding N-tosylhydrazones, which are employed as reaction partners in various transition-metal-catalyzed carbene-based cross-coupling reactions. The N-tosylhydrazone-based carbene couplings significantly enhance the potential of ketones and aldehydes in modern organic synthesis. This Perspective aims to give an overview of carbene coupling reactions with N-tosylhydrazones from the viewpoint of exploring new potentials of ketones and aldehydes in organic synthesis.

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“…Transition metal-catalyzed cross-coupling reactions allow the expansion of bond linkage types through the engagement of innovative catalytic pathways at aromatic ring sites. Numerous electronically and optically active polymers have been fabricated based on this new synthetic modality. , Despite enormous progress, major hurdles remain to prevent their widespread applications: typically required laborious pre-installation of halide substituents, costly synthesis of unstable organometallic intermediates, potential abundance of competitive side reactions, and stoichiometric formation of toxic organometallic byproducts (Scheme a). − …”

Section: Introductionmentioning

confidence: 99%

Rhodium-Catalyzed Redox-Neutral Cross-Dehydrogenative Alkenylation of Arylhydrazines for Polymer Synthesis

Chu

et al. 2021

Macromolecules

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Direct C–H coupling promises to revolutionize the field of polymer synthesis but can be severely plagued by the site selectivity issue. To address this issue, we report herein the development of a directed redox-neutral cross-dehydrogenative C–H cross-coupling polymerization method under transition metal catalysis. A rhodium catalytic protocol is established for arylhydrazine alkenylation polymerization on hydrazine and acrylate coupling partners. The internal oxidant role of the N-amino group ensures its effective directing activity only for one C–H activation event, thus allowing the elimination of defect C–H coupling. The polymerization system reported herein features a simple catalytic component, mild reaction conditions, and a broad monomer and correspondingly polymer and functional scope.

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Palladium-catalyzed carbene coupling of N-tosylhydrazones and arylbromides to synthesize cross-conjugated polymers

Abstract: Palladium-catalyzed cross-coupling reactions of N-tosylhydrazones and arylbromides have been applied for the first time in the synthesis of cross-conjugated polymers, namely poly(arylene-1,1-vinylidene)s (iso-PAVs).

Cited by 23 publications

References 48 publications

A mechanistic investigation of the Pd-catalyzed cross-coupling betweenN-tosylhydrazones and aryl halides

A mechanistic investigation of the Pd-catalyzed cross-coupling betweenN-tosylhydrazones and aryl halides

Transition-Metal-Catalyzed Cross-Coupling with Ketones or Aldehydes via N-Tosylhydrazones

Rhodium-Catalyzed Redox-Neutral Cross-Dehydrogenative Alkenylation of Arylhydrazines for Polymer Synthesis

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