Cryptocatalytic 1,2‐Alkene Migration in a σ‐Alkyl Palladium Diene Complex

Evans, Louise; Fey, Natalie; Lloyd‐Jones, Guy C.; Muñoz, María Paz; Slatford, Paul A.

doi:10.1002/anie.200901468

Cited by 27 publications

(7 citation statements)

References 34 publications

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“…Three new palladacycles were characterized by IR, 1 H-NMR, and elemental analysis. Palladacycles containing aqua and triflate ligands or counterion have attracted much attention due to their high catalytic activities and rich structure variety [25][26][27][28][29]. The presence of water in 1 and 3 were confirmed by IR spectra, which showed a broad peak at 3400 cm À1 .…”

Section: Syntheses Of 1-3mentioning

confidence: 77%

(S)-4-tert-Butyl-2-phenyl-2-oxazoline derived palladacycles as efficient catalysts for the decomposition of P=S pesticides

Yang

Guo

et al. 2010

Journal of Coordination Chemistry

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Three palladacycles with N,N-trans coordination, (S)-{2-[2-(4-tert-butyl)oxazolinyl]phenyl-C 1 ,N}(4-R-pyridine)(aqua) n palladium(II) triflate (R ¼ CF 3 , n ¼ 1, 1; R¼ H, n ¼ 0, 2; R ¼ NMe 2 , n ¼ 1, 3), have been prepared from the respective chloride precursors and were characterized with IR and 1 H-NMR and elemental analyses. The crystal structures of 2 and a pincer complex (S,S)-{2,6-bis[2-(4-iso-propyl)oxazolinyl]phenyl-N,C 1 ,N}bromo-palladium(II) hydrate (5) were determined. For methanolysis of P¼S pesticides, it was found that orthopalladated complexes 1-3 effectively catalyzed the reaction; however, the pincer complex 4 with triflate counterion was much less active. Relative to the methoxide-promoted background reaction at s s pH 10.80, 1 mmol L À1 of palladacycles 1-3 can accelerate the methanolysis by 8.7 Â 10 9 , 1.5 Â 10 9 , and 1.0 Â 10 8 -fold, respectively. For racemic P¼S pesticides, such as letophos and EPN, it proved that there is no clear chiral discrimination during the catalysis. The reaction mechanism of the catalytic methanolysis was discussed according to the experimental results.

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Section: Syntheses Of 1-3mentioning

confidence: 77%

(S)-4-tert-Butyl-2-phenyl-2-oxazoline derived palladacycles as efficient catalysts for the decomposition of P=S pesticides

Yang

Guo

et al. 2010

Journal of Coordination Chemistry

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“…As to versatile 1,1‐D 2 ‐ propargyl alcohol, the reported methods of its synthesis are based on the reduction of acetylenecarboxylic acid esters with LiAlD 4 , with the yields varying from 35 to 86 % . We used an alternative approach, adding magnesium acetylide 10 to deuterated paraformaldehyde (CD 2 O) n to obtain alcoholate 11 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Full Library of (Bis–allyl)‐deuterated Arachidonic Acids: Synthesis and Analytical Verification

et al. 2016

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Deuteration at bis‐allylic positions slows down hydrogen abstraction, thereby reducing the rate of polyunsaturated fatty acids (PUFA) oxidation. Arachidonic acid undergoes oxidation through both enzymatic and non‐enzymatic mechanisms, giving rise to a range of important products with variable biological activity, including pro‐ and anti‐inflammatory properties. We report on the synthesis and verification of a full library of arachidonic acids variably deuterated at the bis‐allylic (C7, C10, C13) positions: 7,7‐D2‐arachidonic acid, 10,10‐D2‐arachidonic acid, 13,13‐D2‐arachidonic acid, 7,7,10,10‐D4‐arachidonic acid, 7,7,13,13‐D4‐arachidonic acid, 10,10,13,13‐D4‐arachidonic acid, and 7,7,10,10,13,13‐D6‐arachidonic acid isotopologues. The library is intended to be useful for determining the relative importance of enzymatic versus non‐enzymatic oxidation at particular sites in vivo.

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“…is generally achieved in situ using a simple salt like PdCl 2 as the metal-containing precursor. In the recent literature there is an increasing amount of examples that palladium catalysis proceeds via the formation of oligonuclear palladium species [8][9][10], casting some doubt on the so far frequent assumption that palladium catalysis involves discrete mononuclear entities. Solid palladium chloride can exist in distinct polymorphic structures.…”

Section: Introductionmentioning

confidence: 99%

Clustering of palladium(II) chloride in acetonitrile solution investigated by electrospray mass spectrometry

Šádek

Schröder

Tsierkezos

2011

International Journal of Mass Spectrometry

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Cryptocatalytic 1,2‐Alkene Migration in a σ‐Alkyl Palladium Diene Complex

Cited by 27 publications

References 34 publications

(S)-4-tert-Butyl-2-phenyl-2-oxazoline derived palladacycles as efficient catalysts for the decomposition of P=S pesticides

(S)-4-tert-Butyl-2-phenyl-2-oxazoline derived palladacycles as efficient catalysts for the decomposition of P=S pesticides

Full Library of (Bis–allyl)‐deuterated Arachidonic Acids: Synthesis and Analytical Verification

Clustering of palladium(II) chloride in acetonitrile solution investigated by electrospray mass spectrometry

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