Introduction to Spatial Anion Control for Direct C–H Arylation

Čorić, Ilija; Dhankhar, Jyoti

doi:10.1055/s-0040-1719860

Cited by 3 publications

(2 citation statements)

References 105 publications

(137 reference statements)

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“…However, in a few cases, significant functionalization next to small alkyl substituents was observed and, in the case of indoprofen methyl ester, arylation next to the methylene group was preferred (Figure 2a, right). Endocyclic methylene substituents are present in a diverse range of pharmaceutically relevant arene classes, but substrate‐limited arylations of non‐activated arenes are rare [49, 58–60] and, in particular, sites ortho to alkyl groups are not readily accessible [48, 49] . Therefore, in order to study the observed selectivity, we started the investigation by using lactone 1 a (phthalide), which possesses an electronically similar arene, but lacks the extended structure of indoprofen, which might potentially influence the selectivity.…”

Section: Figurementioning

confidence: 99%

Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups

et al. 2022

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Catalytic systems for direct CÀ H activation of arenes commonly show preference for electronically activated and sterically exposed CÀ H sites. Here we show that a range of functionally rich and pharmaceutically relevant arene classes can undergo site-selective CÀ H arylation ortho to small alkyl substituents, preferably endocyclic methylene groups. The CÀ H activation is experimentally supported as being the selectivitydetermining step, while computational studies of the transition state models indicate the relevance of noncovalent interactions between the catalyst and the methylene group of the substrate. Our results suggest that preference for C(sp 2 )À H activation next to alkyl groups could be a general selectivity mode, distinct from common steric and electronic factors.

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Section: Figurementioning

confidence: 99%

Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups

et al. 2022

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show abstract

“…[58] However, in a few cases, significant functionalization next to small alkyl substituents was observed and, in the case of indoprofen methyl ester, arylation next to the methylene group was preferred (Figure 2a, right). Endocyclic methylene substituents are present in a diverse range of pharmaceutically relevant arene classes, but substrate-limited arylations of non-activated arenes are rare [49,[58][59][60] and, in particular, sites ortho to alkyl groups are not readily accessible. [48,49] Therefore, in order to study the observed selectivity, we started the investigation by using lactone 1 a (phthalide), which possesses an electronically similar arene, but lacks the extended structure of indoprofen, which might potentially influence the selectivity.…”

mentioning

confidence: 99%

Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups

et al. 2022

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Catalytic systems for direct C−H activation of arenes commonly show preference for electronically activated and sterically exposed C−H sites. Here we show that a range of functionally rich and pharmaceutically relevant arene classes can undergo site‐selective C−H arylation ortho to small alkyl substituents, preferably endocyclic methylene groups. The C−H activation is experimentally supported as being the selectivity‐determining step, while computational studies of the transition state models indicate the relevance of non‐covalent interactions between the catalyst and the methylene group of the substrate. Our results suggest that preference for C(sp2)−H activation next to alkyl groups could be a general selectivity mode, distinct from common steric and electronic factors.

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Control Over Anion Coordination on Pd(II), Cu(I), and Ag(I) with Regioisomeric Phosphine‐Carboxylate Ligands

González‐Fernández,

Marinus,

Dhankhar

et al. 2024

Chemistry A European J

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The coordination of anionic donors is involved at various stages of catalytic cycles in transition‐metal catalysis, but control over the spatial positioning of anions around a metal center is a challenge in coordination chemistry. Here we show that regioisomeric phosphine‐carboxylate ligands provide spatial anion control on palladium(II) centers by favoring either κ2, cis‐κ1, or trans‐κ1 coordination of the carboxylate donor. Additionally, the palladium(II) carboxylates, which contain a methyl donor, upon protonation, deliver metal‐alkyl complexes that feature a coordinated carboxylic acid. Such complexes can be considered as models for the minima that follow the concerted metalation‐deprotonation transition state for C–H activation. The predictability of the coordination modes is further demonstrated on silver(I) and copper(I) centers, for which less common structures of mononuclear and binuclear complexes can be obtained by using spatial anion control. Our results demonstrate the potential for spatial control over carboxylate anions in coordination chemistry.

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Introduction to Spatial Anion Control for Direct C–H Arylation

Cited by 3 publications

References 105 publications

Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups

Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups

Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups

Control Over Anion Coordination on Pd(II), Cu(I), and Ag(I) with Regioisomeric Phosphine‐Carboxylate Ligands

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