Radical arenes

Bednar, Taylor N.; Nagib, David A.

doi:10.1038/s41557-022-01109-6

“…44 A prime example is the C−H functionalization of arenes using triarylsulfonium salt 15, as recently reported by Bednar et al and Procter et al (Scheme 8). 45,46 Mixing 15 with the arene gave the adduct 16, which together with the amine 17 formed EDA complex [17,16], which is characterized by a small red-shifted absorption in the UV−vis spectrum. The subsequent photoinduced SET (λ em = 456 nm) led to the formation of both the amine radical cation 18 and the sulfur radical 19, of which the latter undergoes homolytic bond cleavage to yield the sp 2 -arene radical 20.…”

Section: Photoinduced Single-electron Transfer: Utilization In Synthesismentioning

confidence: 99%

Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor–Acceptor Systems in Main Group Chemistry

Zee

¹

,

Pahar

²

,

Richards

³

et al. 2023

View full text Add to dashboard Cite

The activation and utilization of substrates mediated by Frustrated Lewis Pairs (FLPs) was initially believed to occur solely via a two-electron, cooperative mechanism. More recently, the occurrence of a single-electron transfer (SET) from the Lewis base to the Lewis acid was observed, indicating that mechanisms that proceed via oneelectron-transfer processes are also feasible. As such, SET in FLP systems leads to the formation of radical ion pairs, which have recently been more frequently observed. In this review, we aim to discuss the seminal findings regarding the recently established insights into the SET processes in FLP chemistry as well as highlight examples of this radical formation process. In addition, applications of reported main group radicals will also be reviewed and discussed in the context of the understanding of SET processes in FLP systems.

show abstract

“…The decoration of (hetero)arenes by fluorinated motifs is therefore of high significance to modulate and fine‐tune these interactions. Several key strategies have been reported to install fluorinated substituents onto (hetero)arenes, including oxidation of the (hetero)arenes, [46–48] Minisci‐type reactions [49,50] and direct C Ar −H functionalization [51,52] . The latter strategy is particularly attractive because it is as close to universality as one could imagine, formally allowing the functionalization of any molecule with the only prerequisite that it contains at least one C Ar −H bond [51] .…”

Section: Introductionmentioning

confidence: 99%

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Fernandes,

Giri,

Houk

et al. 2024

View full text Add to dashboard Cite

We highlight key contributions in the field of direct radical CAr–H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into three categories according to the electronic properties of the substrates. Density functional theory computational analysis provides insights into the chemical reactivity of several fluorinated radicals through their electrophilicity and nucleophilicity parameters. Theoretical analysis of their reduction potentials also highlights the remarkable correlation between electrophilicity and oxidizing ability. It is also established that highly fluorinated radicals (e.g.•OCF3) are capable of engaging in single‐electron transfer (SET) processes rather than radical addition, which is in good agreement with experimental literature data. A reactivity scale, based on activation barrier of addition of these radicals to benzene is also elaborated using the high accuracy DLPNO‐(U)CCSD(T) method.

show abstract

“…[43][44][45] The decoration of (hetero)arenes by fluorinated motifs is therefore of high significance to modulate and fine-tune these interactions. Several key strategies have been reported to install fluorinated substituents onto (hetero)arenes, including oxidation of the (hetero)arenes, [46][47][48] Minisci-type reactions [49,50] and direct C Ar À H functionalization. [51,52] The latter strategy is particularly attractive because it is as close to universality as one could imagine, formally allowing the functionalization of any molecule with the only prerequisite that it contains at least one C Ar À H bond.…”

Section: Introductionmentioning

confidence: 99%

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Fernandes,

Giri,

Houk

et al. 2024

Angewandte Chemie

1

0

View full text Add to dashboard Cite

We highlight key contributions in the field of direct radical CAr–H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into three categories according to the electronic properties of the substrates. Density functional theory computational analysis provides insights into the chemical reactivity of several fluorinated radicals through their electrophilicity and nucleophilicity parameters. Theoretical analysis of their reduction potentials also highlights the remarkable correlation between electrophilicity and oxidizing ability. It is also established that highly fluorinated radicals (e.g.•OCF3) are capable of engaging in single‐electron transfer (SET) processes rather than radical addition, which is in good agreement with experimental literature data. A reactivity scale, based on activation barrier of addition of these radicals to benzene is also elaborated using the high accuracy DLPNO‐(U)CCSD(T) method.

show abstract

Radical arenes

Cited by 4 publications

References 12 publications

Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor–Acceptor Systems in Main Group Chemistry

Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor–Acceptor Systems in Main Group Chemistry

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Contact Info

Product

Resources

About

Radical arenes

Cited by 4 publications

References 12 publications

Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor–Acceptor Systems in Main Group Chemistry

Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor–Acceptor Systems in Main Group Chemistry

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

Contact Info

Product

Resources

About

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes