Copper‐Catalyzed Remote C(sp<sup>3</sup>)−H Trifluoromethylation of Carboxamides and Sulfonamides

Liu, Zhonglin; Xiao, Haiwen; Zhang, Benxiang; Shen, Haigen; Zhu, Lin; Li, Chaozhong

doi:10.1002/anie.201813425

Cited by 170 publications

(79 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The photochemically generated Cu II species then traps the alkyl or acyl radical to afford the targeted product. Notably, a catalytic variant of such transformations was disclosed very recently . In addition, the reductive cleavage of the N−F bond by Cu I also allows for the generation of reactive N radicals that can engage in a 1,5‐HAT leading to translocated C radicals that are intercepted by a Cu II CF 3 complex (Figure ).…”

Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

The Persistent Radical Effect in Organic Synthesis

2019

View full text Add to dashboard Cite

Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.

show abstract

Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

The Persistent Radical Effect in Organic Synthesis

2019

View full text Add to dashboard Cite

show abstract

“…The induced magnetic field is related to the shielding tensor by the relation B ind [31,36,[60][61][62] in which i and j are related to the x, y,a nd z axes to account for different representative orientations of the external field B ext .B onding analysis was carried out by using the AdNDP code, [63,64] af lexible tool based on the NBO [65][66][67] analysis and capable of recovering both localized and delocalized bonds to get intuitive Lewis-like pictures. [68][69][70][71][72][73] AdNDP analysis was carried out at the MN15L/def2-TZVP [74,75] and CAM-B3LYP/def2-TZVP [76] levels of theory by using Gaussian 16. [77] Our reoptimization at the MN15L/def2-TZVP level of theory did not change the original geometry [22] significantly and showed its vibrational stability,w hich is full in agreement with the results obtained at the TZ2P-PBE/ZORA level of theory.P reviously,t he MN15L functional was used for bonding analysis in [Pd 3 Sn 8 Bi 6 ] 4À and proven to produce ac redible electronic structure alongside with time-tested PBE0 functional.…”

Section: Computationaldetailsmentioning

confidence: 99%

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu₁₂@Sn₂₀]¹²⁻

Kulichenko

Fedik

Boldyrev

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

Structural characterization of the discrete [Sn@Cu12@Sn20]12− cluster exposed a fascinating architecture composed of three concentric structural layers in which an endohedral Sn atom is enclosed in a Cu12 icosahedron, which in turn is embedded in an Sn20 dodecahedron. Herein, the possibility of sustaining aromatic behavior for this prototypical multilayered species was evaluated, in order to extend this concept to more complex clusters on the basis of magnetic response and bonding analysis by the AdNDP approach. This revealed characteristic features of spherical aromatics, given by the ability to sustain the shielding cone property, similar to archetypal aromatics. The favorable bonding pattern in the [Sn@Cu12@Sn20]12− cluster fulfills the 2(N+1)2 Hirsch rule for aromaticity; thus, the cluster could be regarded as a first member of aromatic multilayered structures. The set of four 13c–2e aromatic bonds that was identified in the internal SnCu12 structure results in spherical aromatic character of this multilayered cluster. This insight builds a bridge between the traditional concept of Hückel's aromaticity and the aromaticity of complex and stable 3D systems that may be explored on the basis of magnetic response and bonding analysis. It also may open a way to novel findings in bottled clusters displaying aromatic behavior in multilayer structures, which are of great interest for inorganic nano‐ and material sciences due to their unprecedented stability.

show abstract

“…Based on these results and previous literatures, we proposed a simplified possible reaction mechanism (Scheme ). The reaction started with the formation of a reduced iron(n) catalyst, which was generated from the reduction of the Fe(acac) 3 pre‐catalyst under standard conditions.…”

Section: Methodsmentioning

confidence: 70%

Iron‐Catalyzed Synthesis of Dihydronaphthalenones from Aromatic Oxime Esters

Zhang

Yin

2019

Adv Synth Catal

View full text Add to dashboard Cite

Herein, a convenient procedure on iron‐catalyzed radical‐mediated synthesis of dihydronaphthalenones from oxime esters has been developed. By using iron salt as a green and inexpensive catalyst, various α‐aryl oxime esters were transformed into the corresponding dihydronaphthalenones in moderate to good yields with high chemo‐selectivities. The reaction proceeds via 1,5‐hydrogen atom transfer and then intramolecular radical cyclization sequence.

show abstract

Copper‐Catalyzed Remote C(sp³)−H Trifluoromethylation of Carboxamides and Sulfonamides

Cited by 170 publications

References 73 publications

The Persistent Radical Effect in Organic Synthesis

The Persistent Radical Effect in Organic Synthesis

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu₁₂@Sn₂₀]¹²⁻

Iron‐Catalyzed Synthesis of Dihydronaphthalenones from Aromatic Oxime Esters

Contact Info

Product

Resources

About

Copper‐Catalyzed Remote C(sp3)−H Trifluoromethylation of Carboxamides and Sulfonamides

Cited by 170 publications

References 73 publications

The Persistent Radical Effect in Organic Synthesis

The Persistent Radical Effect in Organic Synthesis

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu12@Sn20]12−

Iron‐Catalyzed Synthesis of Dihydronaphthalenones from Aromatic Oxime Esters

Contact Info

Product

Resources

About

Copper‐Catalyzed Remote C(sp³)−H Trifluoromethylation of Carboxamides and Sulfonamides

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu₁₂@Sn₂₀]¹²⁻