Mn-Enabled Radical-Based Alkyl–Alkyl Cross-Coupling Reaction from 4-Alkyl-1,4-dihydropyridines

Wang, Jie; Pang, Yubo; Tao, Na; Zeng, Runsheng; Zhao, Yingsheng

doi:10.1021/acs.joc.9b02323

Cited by 14 publications

(4 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…reported a manganese-induced alkyl–alkyl cross-coupling of β-chloroketones with alkyl-DHPs (dihydropyridine) (Scheme ). The use of alkyl-DHPs has the great advantage of their being easily cleaved at the 4-position of C–C to generate alkyl radicals, and these compounds can be easily prepared from aldehydes in a single step . The treatment of β-chloropropiophenone with various alkyl-DHPs in the presence of DTBP (2-( tert -butylperoxy)-2-methylpropane) results in dehydrochlorination.…”

Section: Traditional Cross-coupling Reactionsmentioning

confidence: 99%

Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

Kranthikumar

2022

Organometallics

View full text Add to dashboard Cite

The formation of a new C–C bond at sp3-hybridized centers is highly desirable, as it opens up a unique, unexplored chemical space. The revolutionary discoveries in this field meet the longstanding challenge of forming stereocontrolled C–C bonds and provide rapid access to C(sp3)-rich drug molecules. The new and improved catalytic systems have enabled the creative design of challenging transformations. The latest advancements in nickel catalysis are particularly attractive and have shown excellent catalytic performance in this field. The progress that has been made toward C(sp3)–C(sp3) bond formation (traditional and cross-electrophile couplings) in the past decade is highlighted in this review.

show abstract

Section: Traditional Cross-coupling Reactionsmentioning

confidence: 99%

Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

Kranthikumar

2022

Organometallics

View full text Add to dashboard Cite

show abstract

“…[11] In 2019, we developed a highly efficient alkylation of β-chloro ketones by means of a domino dehydrochlorination / Mn-enabled radical-based alkyl-alkyl cross-coupling reaction (Scheme 1). [12] Here, we report a new development in performing the Csp 3 À Csp 3 Coupling of beta-Chlorophenones. A metal-free bipyridine-catalyzed alkyl-alkyl coupling reaction by a domino dehydrochlorination process.…”

Section: Introductionmentioning

confidence: 99%

A Bipyridine‐Promoted Csp³−Csp³ Coupling of beta‐Chlorophenones

Wang

et al. 2023

Chemistry An Asian Journal

Self Cite

View full text Add to dashboard Cite

A novel, direct Csp 3 À Csp 3 coupling reaction of βchlorophenone with alkanes using 2-(tert-butylperoxy)-2methylpropane (DTBP) as the oxidant and 2,2'-bipyridine (bpy) as the effective additive was developed. A variety of β-chloropropiophenones were well tolerated, and afforded alkylated products in moderate to good yields. A mechanistic study indicated a free radical pathway was involved in this alkyl-alkyl cross-coupling reaction.

show abstract

“…4-Substituted Hantzsch esters (XRH, Scheme ), known as dipine drugs, are used to treat hypertensive and cardiovascular diseases as calcium channel modulators, , which also have the 1,4-dihydropyridine structure and used as excellent NADH coenzyme models. − XRH were investigated as antioxidants to quench active radicals (R • , RO • , ROO • , RS • or RNH • , and so on) in vivo and vitro in many papers. − In recent years, XRH have been examined as alkyl reagents to synthetize various bioactive molecules, and the key elementary step is XRH •+ releasing R • (XRH •+ → XH + + R • ). − However, not all XRH •+ can release R • ; for example, 4-phenyl-Hantzsch ester could not release Ph • itself . We wonder that could XRH •+ be used as H • donors served as radical scavengers just like NADH and NADH •+ (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Quantitative Estimation of the Hydrogen-Atom-Donating Ability of 4-Substituted Hantzsch Ester Radical Cations

et al. 2021

View full text Add to dashboard Cite

The purpose of this study is to investigate thermodynamic and kinetic properties on the hydrogen-atom-donating ability of 4-substituted Hantzsch ester radical cations (XRH •+ ), which are excellent NADH coenzyme models. Gibbs free energy changes and activation free energies of 17 XRH •+ releasing H • [denoted as Δ G HD o (XRH •+ ) and Δ G HD ≠ (XRH •+ )] were calculated using density functional theory (DFT) and compared with that of Hantzsch ester (HEH 2 ) and NADH. Δ G HD o (XRH •+ ) range from 19.35 to 31.25 kcal/mol, significantly lower than that of common antioxidants (such as ascorbic acid, BHT, the NADH coenzyme, and so forth). Δ G HD ≠ (XRH •+ ) range from 29.81 to 39.00 kcal/mol, indicating that XRH •+ spontaneously releasing H • are extremely slow unless catalysts or active intermediate radicals exist. According to the computed data, it can be inferred that the Gibbs free energies and activation free energies of the core 1,4-dihydropyridine radical cation structure (DPH •+ ) releasing H • [Δ G HD o (DPH •+ ) and Δ G HD ≠ (DPH •+ )] should be 19–32 kcal/mol and 29–39 kcal/mol in acetonitrile, respectively. The correlations between the thermodynamic driving force [Δ G HD o (XRH •+ )] and the activation free energy [Δ G HD ≠ (XRH •+ )] are also explored. Gibbs free energy is the important and decisive parameter, and Δ G HD ≠ (XRH •+ ) increases in company with the increase of Δ G HD o (XRH •+ ), but no simple linear correlations are found. Even though all XRH •+ are judged as excellent antioxidants from the thermodynamic view, the computed data indicate that whether XRH •+ is an excellent antioxidant in reaction is decided by the R substituents in 4-position. XRH •+ with nonaromatic substituents tend to release R • instead of H • to quench radicals. XRH •+ with aromatic substituents tend to release H • and be used as antioxidants, but not all aromatic substituted Hantzsch esters are excellent antioxidants.

show abstract

Mn-Enabled Radical-Based Alkyl–Alkyl Cross-Coupling Reaction from 4-Alkyl-1,4-dihydropyridines

Cited by 14 publications

References 44 publications

Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

A Bipyridine‐Promoted Csp³−Csp³ Coupling of beta‐Chlorophenones

Quantitative Estimation of the Hydrogen-Atom-Donating Ability of 4-Substituted Hantzsch Ester Radical Cations

Contact Info

Product

Resources

About

Mn-Enabled Radical-Based Alkyl–Alkyl Cross-Coupling Reaction from 4-Alkyl-1,4-dihydropyridines

Cited by 14 publications

References 44 publications

Recent Advances in C(sp3)–C(sp3) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

Recent Advances in C(sp3)–C(sp3) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

A Bipyridine‐Promoted Csp3−Csp3 Coupling of beta‐Chlorophenones

Quantitative Estimation of the Hydrogen-Atom-Donating Ability of 4-Substituted Hantzsch Ester Radical Cations

Contact Info

Product

Resources

About

Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

A Bipyridine‐Promoted Csp³−Csp³ Coupling of beta‐Chlorophenones