Mononuclear nonheme ferric-peroxo complex in aldehyde deformylation

2005 ◽  
pp. 4529 ◽  
Author(s):  
Jamespandi Annaraj ◽  
Yumi Suh ◽  
Mi Sook Seo ◽  
Sun Ok Kim ◽  
Wonwoo Nam
Keyword(s):  
2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron

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.


2015 ◽  
Vol 112 (52) ◽  
pp. 15856-15861 ◽  
Author(s):  
Piotr J. Mak ◽  
Michael C. Gregory ◽  
Ilia G. Denisov ◽  
Stephen G. Sligar ◽  
James R. Kincaid

Ablation of androgen production through surgery is one strategy against prostate cancer, with the current focus placed on pharmaceutical intervention to restrict androgen synthesis selectively, an endeavor that could benefit from the enhanced understanding of enzymatic mechanisms that derives from characterization of key reaction intermediates. The multifunctional cytochrome P450 17A1 (CYP17A1) first catalyzes the typical hydroxylation of its primary substrate, pregnenolone (PREG) and then also orchestrates a remarkable C17–C20 bond cleavage (lyase) reaction, converting the 17-hydroxypregnenolone initial product to dehydroepiandrosterone, a process representing the first committed step in the biosynthesis of androgens. Now, we report the capture and structural characterization of intermediates produced during this lyase step: an initial peroxo-anion intermediate, poised for nucleophilic attack on the C20 position by a substrate-associated H-bond, and the crucial ferric peroxo-hemiacetal intermediate that precedes carbon–carbon (C-C) bond cleavage. These studies provide a rare glimpse at the actual structural determinants of a chemical transformation that carries profound physiological consequences.


2012 ◽  
Vol 51 (22) ◽  
pp. 5427-5430 ◽  
Author(s):  
Chien-Ming Lee ◽  
Chi-He Chuo ◽  
Ching-Hui Chen ◽  
Cho-Chun Hu ◽  
Ming-Hsi Chiang ◽  
...  

ChemInform ◽  
2003 ◽  
Vol 34 (40) ◽  
Author(s):  
Subhabrata Das ◽  
Tandra Bhowmick ◽  
T. Punniyamurthy ◽  
Deepa Dey ◽  
Jayashree Nath ◽  
...  

2017 ◽  
Vol 531 ◽  
pp. 45-51 ◽  
Author(s):  
Sonali B. Khomane ◽  
Dhananjay S. Doke ◽  
M.K. Dongare ◽  
S.B. Halligudi ◽  
S.B. Umbarkar

RSC Advances ◽  
2018 ◽  
Vol 8 (27) ◽  
pp. 15196-15201 ◽  
Author(s):  
Xiang-Yun Wang ◽  
Hui-Min Yan ◽  
Yan-Li Han ◽  
Zhu-Xia Zhang ◽  
Xiao-Yun Zhang ◽  
...  

Density functional theory calculations were performed in order to reveal the mysterious catalytic step of the biosynthesis of estrogens.


ChemPlusChem ◽  
2015 ◽  
Vol 80 (6) ◽  
pp. 1029-1037 ◽  
Author(s):  
Jizhong Chen ◽  
Li Hua ◽  
Chen Chen ◽  
Li Guo ◽  
Ran Zhang ◽  
...  

2016 ◽  
Vol 129 (3) ◽  
pp. 819-823 ◽  
Author(s):  
Seong Hee Bae ◽  
Yong‐Min Lee ◽  
Shunichi Fukuzumi ◽  
Wonwoo Nam

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