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Hydrogen Bonding-Assisted and Nonheme Manganese-Catalyzed Remote Hydroxylation of C-H Bonds in Nitrogen-Containing Molecules
- Title
- Hydrogen Bonding-Assisted and Nonheme Manganese-Catalyzed Remote Hydroxylation of C-H Bonds in Nitrogen-Containing Molecules
- Authors
- Chen J.; Song W.; Yao J.; Wu Z.; Lee Y.-M.; Wang Y.; Nam W.; Wang B.
- Ewha Authors
- 남원우; 이용민
- SCOPUS Author ID
- 남원우
; 이용민![scopus](/images/layout/icon2.png)
![scopus](/images/layout/icon2.png)
![scopus](/images/layout/icon2.png)
- Issue Date
- 2023
- Journal Title
- Journal of the American Chemical Society
- ISSN
- 0002-7863
- Citation
- Journal of the American Chemical Society vol. 145, no. 9, pp. 5456 - 5466
- Publisher
- American Chemical Society
- Indexed
- SCIE; SCOPUS
![scopus](/images/layout/scopus2.gif)
- Document Type
- Article
- Abstract
- The development of catalytic systems capable of oxygenating unactivated C-H bonds with excellent site-selectivity and functional group tolerance under mild conditions remains a challenge. Inspired by the secondary coordination sphere (SCS) hydrogen bonding in metallooxygenases, reported herein is an SCS solvent hydrogen bonding strategy that employs 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as a strong hydrogen bond donor solvent to enable remote C-H hydroxylation in the presence of basic aza-heteroaromatic rings with a low loading of a readily available and inexpensive manganese complex as a catalyst and hydrogen peroxide as a terminal oxidant. We demonstrate that this strategy represents a promising compliment to the current state-of-the-art protection approaches that rely on precomplexation with strong Lewis and/or Brønsted acids. Mechanistic studies with experimental and theoretical approaches reveal the existence of a strong hydrogen bonding between the nitrogen-containing substrate and HFIP, which prevents the catalyst deactivation by nitrogen binding and deactivates the basic nitrogen atom toward oxygen atom transfer and the α-C-H bonds adjacent to the nitrogen center toward H-atom abstraction. Moreover, the hydrogen bonding exerted by HFIP has also been demonstrated not only to facilitate the O-O bond heterolytic cleavage of a putative MnIII-OOH precursor to generate MnV(O)(OC(O)CH2Br) as an active oxidant but also to affect the stability and the activity of MnV(O)(OC(O)CH2Br). © 2023 American Chemical Society.
- DOI
- 10.1021/jacs.2c13832
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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