Palladium−Ruthenium Catalyst Complementarity Strengthens <i>Ortho</i>‐Directed C−H Bond Arylation of 2‐Arylpyrazines

Benzai, Amal; Derridj, Fazia; Doucet, Henri

doi:10.1002/cctc.202001338

Cited by 5 publications

(4 citation statements)

References 68 publications

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“…On the other hand, since diazine motifs are important building blocks in a variety of fields, it is of high interest and urgency to further develop technologies to circumvent the poor reactivity encountered not to mention to address selectivity issues when multiple C-H sites are available for reaction. Interestingly, as diazines are also used as directing groups for C-H functionalizations, [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74] examples merging this strategy with direct C-H functionalization at the diazine core in a one-pot or cascade manner might be appealing to undertake. 75 With this review, we hope to stimulate the scientific community to developing efficient tools to tackle C-H functionalizations of diazines en route to complex structures.…”

Section: Discussionmentioning

confidence: 99%

Carbon–Carbon Bond Forming Reactions in Diazines via Transition-Metal-Catalyzed C–H Bond Activation

Gramage‐Doria

Bruneau²

2023

Synthesis

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An overview of the key achievements concerning carbon-carbon bond-forming process with diazines under transition metal-catalyzed C-H activation is presented. Focus is devoted to those examples in which the C-H functionalization takes place in the diazine or the benzodiazine core because of its relevance in material sciences and as active pharmaceutical ingredients. These metal-catalyzed protocols take benefit from the biased reactivity of the C-H bonds targeted or from the presence of a rationally-designed directing group at proximity of the C-H bond to be functionalized. As such, innovative alkylations, alkenylations, alkynylations, arylations and carboxylations are accomplished within such skeletons in a step- and atom-economy fashion.

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Section: Discussionmentioning

confidence: 99%

Carbon–Carbon Bond Forming Reactions in Diazines via Transition-Metal-Catalyzed C–H Bond Activation

Gramage‐Doria

Bruneau²

2023

Synthesis

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“…The [RuCl 2 (p-cym)] 2 catalyst exhibited poor catalytic performance during ortho C-H mono-arylation of 2,3-diphenylpyrazine with electron-deficient 4-bromonitrobenzene and gave the product in only 15% isolated yield. 45 In sharp contrast, the developed method B delivered the desired product 3h in good yield (74%). The F group on 2 was tolerated under both reaction conditions and afforded the corresponding ortho mono-arylation product 3i in decent yield.…”

Section: Paper Synthesismentioning

confidence: 96%

“…36 Thus, the interchange of the first two steps depending on the identity of the transition metal center could allow complementary reactivity of directed ortho C–H arylation with haloarenes. 45…”

Section: Table 1 Representative Data Of the Optimizatio...mentioning

confidence: 99%

“…36 Thus, the interchange of the first two steps depending on the identity of the transition metal center could allow complementary reactivity of directed ortho C-H arylation with haloarenes. 45 Herein, we report Pd(II)-and Ru(II)-catalyzed ortho C-H monoarylation of 2-arylbenzoxazole/thiazole scaffolds to address the synthetic drawbacks mentioned above.…”

Section: Paper Synthesismentioning

confidence: 99%

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Benzoxazole or Benzothiazole as an Innate Directing Group for Palladium- and Ruthenium-Catalyzed Complementary C–H Arylation: Functionalization of Biorelevant Heterocyclic Scaffolds

Seth,

Maingle,

Sunny

et al. 2023

Synthesis

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Benzoxazole and benzothiazole moiety have been used as innate directing handles for Pd(II)- and Ru(II)-catalyzed C–H arylation of bio-relevant heterocycles, 2-arylbenzoxazole and 2-arylbenzothiazole with diverse iodoarenes, following a complementarity of palladium-ruthenium catalysts. The induction of σ-donor ligands, such as N,N-dimethylacetamide to Pd(II) catalytic cycle and σ-donor/π-acceptor ligand, such as PPh3 to Ru(II) catalytic cycle enhances the arylation rate significantly and governed by the C–H acidity of C2-aryl ring of 2-arylbenzoxazole/2-arylbenzothiazole. The approaches have a broad substrate scope with respect to coupling partners to accommodate electron-neutral, electron-rich as well as electron-deficient iodoarenes plus C2-aryl unit of 2-arylbenzoxazoles/2-arylbenzothiazoles, exhibit a high degree of siteselectivity at ortho-C–H position, afford only mono-arylated derivatives in decent yields, functional groups tolerant, and applicable to ‘gram-scale’ production.

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Ruthenium‐Catalyzed ortho ‐CH Bond Arylation Reactions

Bruneau¹,

Gramage‐Doria²

2022

Handbook of CH-Functionalization

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The highly selective ruthenium-catalyzed ortho-C-H bond arylations have met a level of maturity that makes them an attractive tool to achieve unique organic transformations.By means of the manifold mechanisms operating in the presence of different arylating agents and reaction conditions, these methodologies have succeeded in reducing the wastes/steps towards the desired molecules as well as enlarging the chemical space by affording molecules impossible to obtain otherwise. The key achievements in this area are discussed in this chapter. Introduction.Biaryl and terphenyl cores are widespread structures in many biologically active substances and have useful physical properties in material sciences. The seminal results on the synthesis of biphenyl by connecting two aryl iodide molecules via reductive coupling in the presence of copper were reported in 1901 [1] and this concept was further developed [2,3]. Since this discovery, continuous efforts have been devoted to the improvement of these aryl-aryl couplings, mainly based on palladium-catalyzed cross-coupling reactions of aryl (pseudo)halides with organometallic reagents leading to the formation of a new C(sp 2 )-C(sp 2 ) bonds (Figure 1a) [4][5][6][7][8].

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Palladium−Ruthenium Catalyst Complementarity Strengthens Ortho‐Directed C−H Bond Arylation of 2‐Arylpyrazines

Cited by 5 publications

References 68 publications

Carbon–Carbon Bond Forming Reactions in Diazines via Transition-Metal-Catalyzed C–H Bond Activation

Carbon–Carbon Bond Forming Reactions in Diazines via Transition-Metal-Catalyzed C–H Bond Activation

Benzoxazole or Benzothiazole as an Innate Directing Group for Palladium- and Ruthenium-Catalyzed Complementary C–H Arylation: Functionalization of Biorelevant Heterocyclic Scaffolds

Ruthenium‐Catalyzed ortho ‐CH Bond Arylation Reactions

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