Photoredox catalysis in nickel-catalyzed C–H functionalization

Mantry, Lusina; Maayuri, Rajaram; Kumar, Vikash; Gandeepan, Parthasarathy

doi:10.3762/bjoc.17.143

Cited by 30 publications

(13 citation statements)

References 142 publications

(239 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The CCA with SIQPII may not support reversibility of ψ NC-phenyl ≠ ψ 2NC-pyz ≠ ψ NIQ mutually due to different electronic states that attract the NaCl (Figure 13(b)). The CCA as a stabilizer with higher PE and lower KE led to (10) With CCA, the KE = 0, so eq 10 becomes . The energy (E) could be of pyz and NIQ as a NaCl with respective ions stabilizes the secondary and tertiary TS with deficient electronic oscillations.…”

Section: Mechanism Ofmentioning

confidence: 99%

Spiroheterocyclic Photocatalyst for Reducing QHIn-Persistent Pollutants, Dyes, and Transition-Metal Ions Cocatalyzed with Electrolytes

Kumari

Singh

2022

ACS Omega

View full text Add to dashboard Cite

dicarbonitrile (SIQPIII) were used to photocatalyze quinonoid phenolphthalein (QHIn) in aq-ACN-EtOH (mixed solvent) with NaCl and KCl electrolytes. SIQPI, II, and III spiroindenoquinoxaline pyrrolidines (SIQPs) as spiroheterocyclic photocatalysts alone could not reduce QHIn, but with the addition of electrolytes they are reduced via π cationic interactions (PCI). SIQPI, II, and III with NaCl reduced QHIn in 120, 28, and 50 min, unlike in 138, 58, and 63 min with KCl in mixed solvent. SIQPI, II, and III alone have reduced methylene blue (MB) in 120, 45, and 70 min, unlike in 110, 27, and 55 min with graphene oxide (GO), whereas with NaCl and KCl hey are reduced in 82, 36, and 44 min and 89, 43, and 50 min, respectively. SIQPs with GO had reduced MB in less time than the SIQPs alone, and SIQPs with NaCl had reduced QHIn in a shorter time than KCl. The electrolytes have cocatalyzed a reduction of dyes under sunlight (SL). The electrolytes have reduced a quinonoid structure (QS) and dyes by generating negative and positive (e − and h + ) holes in a shorter time. SIQPII and magnetic nanoparticles (MNPs) of 58 nm with NaCl photocatalyzed the QHIn in 2880 min. The SIQPs also reduced methyl orange (MO) and brilliant blue R (BBR) at variable temperature (T) and pH range, whereas SIQPs have developed a molecular organic framework (MOF) with transition-metal salts (NiCl 2 , CrO 3 , KMnO 4 , CuSO 4 , and MnCl 2 ) on photocatalysis.

show abstract

Section: Mechanism Ofmentioning

confidence: 99%

Spiroheterocyclic Photocatalyst for Reducing QHIn-Persistent Pollutants, Dyes, and Transition-Metal Ions Cocatalyzed with Electrolytes

Kumari

Singh

2022

ACS Omega

View full text Add to dashboard Cite

show abstract

“…With the increasing demand of sustainable development, use of the sp 3 C–H bond function in chemical synthesis has received great attention because it can provide a practical solution to upgrade abundant hydrocarbon raw materials into valuable products. − The hydrogen atom transfer (HAT)-based method provides an effective strategy for hydrocarbon activation and has been widely used. ,− However, the prediction of reactivity is still a challenge. The reactivity is closely related to the C–H bond strength and the choice of H-extracting radicals. − Understanding the reaction mechanisms and predicting the reactivity should assist a more reasonable and effective design of C–H activation reactions. − …”

Section: Introductionmentioning

confidence: 99%

Rapid and Accurate Estimation of Activation Free Energy in Hydrogen Atom Transfer-Based C–H Activation Reactions: From Empirical Model to Artificial Neural Networks

Wang

Cao

et al. 2022

ACS Omega

View full text Add to dashboard Cite

A well-performing machine learning (ML) model is obtained by using proper descriptors and artificial neural network (ANN) algorithms, which can quickly and accurately predict activation free energy in hydrogen atom transfer (HAT)-based sp 3 C–H activation. Density functional theory calculations (UωB97X-D) are used to establish the reaction system data sets of methoxyl (CH 3 O·), trifluoroethoxyl (CF 3 CH 2 O·), tert -butoxyl (tBuO·), and cumyloxyl (CumO·) radicals. The simplified Roberts’ equation proposed in our recent study works here [ R 2 = 0.84, mean absolute error (MAE) = 0.85 kcal/mol]. Its performance is comparable with univariate Mulliken-type electronegativity (χ) with the ANN model. The ANN model with bond dissociation free energy, χ, α-unsaturation, and Nolan buried volume (% V buried ) successively improves R 2 and MAE to 0.93 and 0.54 kcal/mol, respectively. It reproduces the test sets of trichloroethoxyl (CCl 3 CH 2 O·) with R 2 = 0.87 and MAE = 0.89 kcal/mol and accurately predicts the relative experimental barrier of the HAT reactions with CumO· and the site selectivity of CH 3 O·.

show abstract

“…Regioselective radical addition of the sulfonyl radical to an electron-deficient alkene 1 will then generate the adduct radical A [66][67][68][69] . On the other hand, oxidative addition of Ni(0) to an aromatic bromide 2 leads to an Ar-Ni-Br complex [70][71][72][73] . Trapping of radical A by the Ar-Ni-Br species will provide the corresponding Ar-Ni(III)-alkyl intermediate, and subsequent reductive elimination will deliver the intermediate D along with a Ni(I) complex [74][75][76][77] .…”

mentioning

confidence: 99%

Cooperative triple catalysis enables regioirregular formal Mizoroki–Heck reactions

2022

View full text Add to dashboard Cite

The Mizoroki–Heck reaction between alkenes and aryl halides represents one of the most important methods for C−C bond formation in synthetic chemistry. Governed by their electronic and steric nature, alkenes are generally arylated with high regioselectivity, which conversely hampers diversity, in particular, if the regioirregular isomer is targeted. Usually, electron-poor alkenes selectively afford the corresponding β-coupled products, and achieving the opposite regioselectivity to obtain their α-arylated congeners is highly challenging. It would be desirable to access the irregular α-regioisomer by simple variation of the reaction conditions, keeping the standard substrates, thereby significantly enlarging the product space. Herein, we describe an intermolecular α-arylation of electron-poor alkenes through cooperative nickel, photoredox and sulfinate catalysis. This triple catalysis system operates under mild conditions and features excellent functional group tolerance. The orchestration of radical, transition metal and ionic bond-forming and -cleaving reactions in a single process is highly challenging, but certainly opens valuable doors in terms of reactivity. Moreover, the intermolecular α-arylation, α-alkenylation and α-alkynylation of styrenes could also be achieved through a one-pot process.

show abstract

Photoredox catalysis in nickel-catalyzed C–H functionalization

Cited by 30 publications

References 142 publications

Spiroheterocyclic Photocatalyst for Reducing QHIn-Persistent Pollutants, Dyes, and Transition-Metal Ions Cocatalyzed with Electrolytes

Spiroheterocyclic Photocatalyst for Reducing QHIn-Persistent Pollutants, Dyes, and Transition-Metal Ions Cocatalyzed with Electrolytes

Rapid and Accurate Estimation of Activation Free Energy in Hydrogen Atom Transfer-Based C–H Activation Reactions: From Empirical Model to Artificial Neural Networks

Cooperative triple catalysis enables regioirregular formal Mizoroki–Heck reactions

Contact Info

Product

Resources

About