Mechanistic Insights into the PdII‐Catalyzed Chemoselective N‐Demethylation vs. Cyclometalation Reactivity Pathways in 1‐Aryl‐N,N‐dimethylethanamines

Yap, Jeanette See Leng; Ding, Yi; Yang, Xiang‐Yuan; Wong, Jen It; Li, Yongxin; Pullarkat, Sumod A.; Leung, Pak‐Hing

doi:10.1002/ejic.201402547

Cited by 6 publications

(1 citation statement)

References 49 publications

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“…175 The proposed mechanism, which is a little different from the above Zhu mechanism, 167 189 A mechanism involving the elimination of the β-amino group in the presence of H 2 O was presented. 190 Initially, the amine would coordinate to the Pd center with the activation of a C−H bond and the formation of a Pd−C bond. Then a nucleophilic attack of OH − from water on the α-C will generate the complex 199, which will give the Pd(0) species and the secondary amine.…”

Section: C−n Bond Cleavage Via Imine or Iminiummentioning

confidence: 99%

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

et al. 2015

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Section: C−n Bond Cleavage Via Imine or Iminiummentioning

confidence: 99%

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

et al. 2015

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Arylene‐Ethynylene Oligomers Based on the Proton Sponge

et al. 2019

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A new family of arylene‐ethynylene oligomers consisting of two, three and four “proton sponge” fragments (1,8‐bis(dimethylamino)naphthalene or DMAN) alternating with C≡C bonds were synthesized using various 2‐ and 4‐ethynyl and 2‐ and 4‐iodo derivatives of DMAN as synthetic building blocks in the Sonogashira coupling. X‐ray structural, photophysical, chemical and electrochemical properties showed that the oligomers are promising candidates to construct materials with varied rigidity (tuned by protonation), electron conductivity (tuned by mode of linkage), and proton conductivity (equilibration of protonated and free DMAN subunits).

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Understanding Anionic “Ligandless” Palladium Species in the Mizoroki–Heck Reaction

Schroeter

Straßner

2018

Inorg. Chem.

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The anionic complex [NBu][Pd(DMSO)Cl], as a "ligandless" system, was shown to be an active catalyst in the Mizoroki-Heck coupling of aryl chlorides in the absence of strongly σ-donating ligands. To investigate the experimentally observed influence of halides and the amount of water on the catalytic activity, we employed a combination of experiments and theoretical calculations. The presence of water was shown to be critical for the formation of the active palladium(0) species by oxidation of in situ generated tributylamine. Oxidative addition to an anionic palladium(0) species was found to be the rate-determining step of the catalytic cycle. For the ensuing steps, both neutral and anionic pathways were considered. It was shown that, in the absence of strongly σ-donating neutral ligands, chloride ions stabilize the catalytic intermediates. Therefore, an anionic pathway is preferred, which explains the need for tetrabutylammonium chloride as an additive. The study of the influence of bromide ions on the catalytic activity revealed that the strongly exergonic displacement of the neutral substrates by bromide ions lowers the catalytic activity.

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Mechanistic Insights into the Pd^II‐Catalyzed Chemoselective N‐Demethylation vs. Cyclometalation Reactivity Pathways in 1‐Aryl‐N,N‐dimethylethanamines

Cited by 6 publications

References 49 publications

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

Arylene‐Ethynylene Oligomers Based on the Proton Sponge

Understanding Anionic “Ligandless” Palladium Species in the Mizoroki–Heck Reaction

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