Mechanistic studies of phosphorus-oxygen bond cleavages in group 7 dinuclear complexes of 2-pyridyl dimethylphosphinite

1986 ◽  
Vol 108 (9) ◽  
pp. 2333-2340 ◽  
Author(s):  
David B. Collum ◽  
Jeffrey A. Klang ◽  
Randall T. Depue
Keyword(s):  
Dinuclear Complexes ◽  
Mechanistic Studies ◽  
Oxygen Bond

Cofactor characterization and mechanistic studies of CDP-6-deoxy-.DELTA.3,4-glucoseen reductase: Exploration into a novel enzymic carbon-oxygen bond cleavage event

Biochemistry ◽  
1993 ◽  
Vol 32 (44) ◽  
pp. 11934-11942 ◽  
Author(s):  
Vaughn P. Miller ◽  
Jon S. Thorson ◽  
Olivier Ploux ◽  
Stanley F. Lo ◽  
Hung Wen Liu
Keyword(s):  
Bond Cleavage ◽  
Mechanistic Studies ◽  
Oxygen Bond

scholarly journals Tactics for probing aryne reactivity: mechanistic studies of silicon–oxygen bond cleavage during the trapping of (HDDA-generated) benzynes by silyl ethers

2014 ◽  
Vol 5 (2) ◽  
pp. 545-550 ◽  
Author(s):  
Thomas R. Hoye ◽  
Beeraiah Baire ◽  
Tao Wang
Keyword(s):  
Bond Cleavage ◽  
Mechanistic Studies ◽  
Silyl Ethers ◽  
Oxygen Bond ◽  
Silicon Oxygen ◽  
Clock Reaction

Mechanistic features of the trapping reaction of an HDDA-generated aryne by pendant silyl ethers were probed using, e.g., an intramolecular clock reaction (cf. k2).

scholarly journals Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne “click reaction”

2015 ◽  
Vol 1 (5) ◽  
pp. e1500304 ◽  
Author(s):  
Liqun Jin ◽  
Daniel R. Tolentino ◽  
Mohand Melaimi ◽  
Guy Bertrand
Keyword(s):  
Direct Observation ◽  
Copper Complexes ◽  
Click Reaction ◽  
Life Sciences ◽  
Dipolar Cycloaddition ◽  
Dinuclear Complexes ◽  
Chemical Transformations ◽  
Terminal Alkyne ◽  
Mechanistic Studies ◽  
Copper Acetylide

The copper-catalyzed 1,3-dipolar cycloaddition of an azide to a terminal alkyne (CuAAC) is one of the most popular chemical transformations, with applications ranging from material to life sciences. However, despite many mechanistic studies, direct observation of key components of the catalytic cycle is still missing. Initially, mononuclear species were thought to be the active catalysts, but later on, dinuclear complexes came to the front. We report the isolation of both a previously postulated π,σ-bis(copper) acetylide and a hitherto never-mentioned bis(metallated) triazole complex. We also demonstrate that although mono- and bis-copper complexes promote the CuAAC reaction, the dinuclear species are involved in the kinetically favored pathway.

DV-Xα calculations on some metallacyclopentadienyl dinuclear complexes

1989 ◽  
Vol 86 ◽  
pp. 841-846 ◽  
Author(s):  
Maurizio Casarin ◽  
Gaetano Granozzi
Keyword(s):  
Dinuclear Complexes

Temporal and mechanistic studies on the resistance of glioma cells to temozolomide

2016 ◽  
Vol 228 (06/07) ◽  
Author(s):  
WP Roos ◽  
M Eich ◽  
S Quiros ◽  
AV Knizhnik ◽  
T Nikolova ◽  
...  
Keyword(s):  
Glioma Cells ◽  
Mechanistic Studies

Oxygen-Oxygen Bond Cleavage and Formation in Co(II) Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical

2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron
Keyword(s):  
Bond Cleavage ◽  
Peroxo Complex ◽  
Oxygen Oxygen ◽  
O2 Reduction ◽  
Oxygen Bond ◽  
Pentadentate Ligand

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.

Bringing Biocatalysis into the Deuteration Toolbox

2019 ◽  
Author(s):  
Jack Rowbotham ◽  
Oliver Lenz ◽  
Holly Reeve ◽  
Kylie Vincent
Keyword(s):  
Late Stage ◽  
Hydrogen Isotope ◽  
Reductive Amination ◽  
Mechanistic Studies ◽  
Ambient Conditions ◽  
Synthetic Pathway ◽  
Drug Candidates ◽  
Isotopic Selectivity ◽  
Reducing Equivalents

<p></p><p>Chemicals labelled with the heavy hydrogen isotope deuterium (<sup>2</sup>H) have long been used in chemical and biochemical mechanistic studies, spectroscopy, and as analytical tracers. More recently, demonstration of selectively deuterated drug candidates that exhibit advantageous pharmacological traits has spurred innovations in metal-catalysed <sup>2</sup>H insertion at targeted sites, but asymmetric deuteration remains a key challenge. Here we demonstrate an easy-to-implement biocatalytic deuteration strategy, achieving high chemo-, enantio- and isotopic selectivity, requiring only <sup>2</sup>H<sub>2</sub>O (D<sub>2</sub>O) and unlabelled dihydrogen under ambient conditions. The vast library of enzymes established for NADH-dependent C=O, C=C, and C=N bond reductions have yet to appear in the toolbox of commonly employed <sup>2</sup>H-labelling techniques due to requirements for suitable deuterated reducing equivalents. By facilitating transfer of deuterium atoms from <sup>2</sup>H<sub>2</sub>O solvent to NAD<sup>+</sup>, with H<sub>2</sub> gas as a clean reductant, we open up biocatalysis for asymmetric reductive deuteration as part of a synthetic pathway or in late stage functionalisation. We demonstrate enantioselective deuteration via ketone and alkene reductions and reductive amination, as well as exquisite chemo-control for deuteration of compounds with multiple unsaturated sites.</p><p></p>

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