期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 1, 页码 46-52出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c09688
关键词
-
资金
- NIH [GM119374]
The study found that non-heme iron complexes exhibit different reactivity with a tertiary carbon radical, providing a new working model for C-S bond formation in isopenicillin N synthase. The results suggest that kinetic control may play a crucial role in the selectivity of non-heme iron rebound processes.
Non-heme iron complexes with cis-Fe-III(OH)(SAr/OAr) coordination were isolated and examined for their reactivity with a tertiary carbon radical. The sulfur-ligated complex shows a temperature dependence on (OH)-O-center dot versus ArS center dot transfer, whereas the oxygen-ligated complex does not. These results provide the first working model for C-S bond formation in isopenicillin N synthase and indicate that kinetic control may be a key factor in the selectivity of non-heme iron rebound processes.
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