Alkyl carbon-oxygen bond cleavage in the hydrolysis of imidate esters to amides in acid solution

1974 ◽  
Vol 96 (11) ◽  
pp. 3690-3691 ◽  
Author(s):  
Robert A. McClelland
Keyword(s):  
Acid Solution ◽  
Bond Cleavage ◽  
Hydrolysis Of ◽  
Oxygen Bond

scholarly journals A novel mechanism of enzymic ester hydrolysis. Inversion of configuration and carbon-oxygen bond cleavage by secondary alkylsulphohydrolases from detergent-degrading micro-organisms

1977 ◽  
Vol 165 (3) ◽  
pp. 575-580 ◽  
Author(s):  
B Bartholomew ◽  
K S Dodgson ◽  
G W J Matcham ◽  
D J Shaw ◽  
G F White
Keyword(s):  
Bond Cleavage ◽  
Hydrolytic Enzymes ◽  
Ester Hydrolysis ◽  
Enzymic Hydrolysis ◽  
Hydrolysis Products ◽  
Bond Scission ◽  
Micro Organisms ◽  
Hydrolysis Of ◽  
Oxygen Bond ◽  
Comamonas Terrigena

The hydrolysis was studied of potassium (+)-octan-2-yl sulphate by two analogous, optically stereospecific, secondary alkylsulphohydrolases purified from two detergent-degrading micro-organisms, Comamonas terrigena and Pseudomonas C12B. Polarimetry studies have shown that (+)-octan-2-yl sulphate prepared from (+)-octan-2-ol is hydrolysed by both enzymes to yield (-)-octan-2-ol. This inversion of configuration implies that the enzymes are catalysing the scission of the C-O bond of the C-O-S linkage, a type of bond scission apparently not hitherto encountered among hydrolytic enzymes acting on ester bonds. Enzymic hydrolysis of potassium (+)-octan-2-yl sulphate in the presence of H218O and analysis of hydrolysis products for the presence of 18O has confirmed that C-O bond scission (and not O-S bond scission) occurs with both enzymes.

The Reactivity-Hydrolysis Relationship in Chemical Finishing of Cotton

1969 ◽  
Vol 39 (8) ◽  
pp. 774-780 ◽  
Author(s):  
Sidney L. Vail
Keyword(s):  
Bond Cleavage ◽  
Urea Formaldehyde ◽  
Electronic Effects ◽  
Acidic Conditions ◽  
The Relationship ◽  
Hydrolysis Of ◽  
Oxygen Bond ◽  
Intermediate Bond ◽  
Substituted Urea

The reactivity-hydrolysis relationship in chemical finishing of cotton with N-methyloltype reactants under acidic conditions has been discussed. Theoretical and practical justifications for the relationship have been presented to demonstrate that the ease of formation of links is related directly to the ease of hydrolysis of links, and relative rates in both directions are predictable, based on steric and electronic effects on the resonance-stabilized intermediate. Bond cleavage during hydrolysis has been shown to occur first at the carbon-oxygen bond of the methylol groups, whether or not the link was formed from a substituted urea-formaldehyde adduct or a substituted urea-glyoxal adduct. Limitations for the relationship are also discussed.

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.

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