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).

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.

scholarly journals Selective Formation of an FeIV O or an FeIII OOH Intermediate From Iron(II) and H2 O2 : Controlled Heterolytic versus Homolytic Oxygen-Oxygen Bond Cleavage by the Second Coordination Sphere

2018 ◽  
Vol 131 (3) ◽  
pp. 864-868 ◽  
Author(s):  
Khaled Cheaib ◽  
M. Qadri E. Mubarak ◽  
Katell Sénéchal-David ◽  
Christian Herrero ◽  
Régis Guillot ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Bond Cleavage ◽  
Oxygen Oxygen ◽  
Second Coordination Sphere ◽  
Selective Formation ◽  
Oxygen Bond

scholarly journals Controlling Non-Native B12 Reactivity and Catalysis in the Transcription Factor CarH

2021 ◽  
Author(s):  
Xinhang Yang ◽  
Benjamin H. R. Gerroll ◽  
Yuhua Jiang ◽  
Amardeep Kumar ◽  
Yasmine S. Zubi ◽  
...  
Keyword(s):  
Transcription Factor ◽  
Vitamin B12 ◽  
Transcription Regulation ◽  
Bond Cleavage ◽  
Oxidative Addition ◽  
Mechanistic Studies ◽  
Organic Transformations ◽  
Carbon Bond ◽  
Wide Range ◽  
Hydride Elimination

Vitamin B12 derivatives catalyze a wide range of organic transformations, but B12-dependent enzymes are underutilized in biocatalysis relative to other metalloenzymes. In this study, we engineered a variant of the transcription factor CarH, called CarH*, that catalyzes styrene C-H alkylation with improved yield and selectivity relative to B12 itself. While the native function of CarH involves transcription regulation via AdoCbl Co(III)-carbon bond cleavage and β-hydride elimination to generate 4’,5’-didehydroadenosine, CarH*-catalyzed styrene alkylation proceeds via non-native oxidative addition and olefin addition coupled with a native-like β-hydride elimination. Mechanistic studies on this reaction echo findings from earlier studies on AdoCbl homolysis under strong cage conditions to suggest that CarH* can enable non-native radical chemistry with improved selectivity relative to B12 itself. These findings lay the groundwork for the development of B12-dependent enzymes as catalysts for a wide range of non-native transformations.

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