BROWSE

Related Scientist

Felix Mulks, Florian's photo.

Felix Mulks, Florian
분자활성 촉매반응 연구단
more info

ITEM VIEW & DOWNLOAD

How To Enhance the Efficiency of Breslow Intermediates for SET Catalysis

Cited 0 time in webofscience Cited 0 time in scopus
106 Viewed 0 Downloaded
Title
How To Enhance the Efficiency of Breslow Intermediates for SET Catalysis
Author(s)
Florian F. Mulks; Mohand Melaimi; Xiaoyu Yan; Mu-Hyun Baik; Guy Bertrand
Publication Date
2023-02
Journal
Journal of Organic Chemistry, v.88, no.4, pp.2535 - 2542
Publisher
American Chemical Society
Abstract
Oxidative carbene organocatalysis, which proceeds via single electron transfer (SET) pathways, has been limited by the moderately reducing properties of deprotonated Breslow intermediates BI-s derived from thiazol-2-ylidene 1 and 1,2,4-triazolylidene 2. Using computational methods, we assess the redox potentials of BI-s based on ten different types of known stable carbenes and report our findings concerning the key parameters influencing the steps of the catalytic cycle. From the calculated values of the first oxidation potential of BI-s derived from carbenes 1 to 10, it appears that, apart from the diamidocarbene 7, all the others are more reducing than thiazol-2-ylidene 1 and the 1,2,4-triazolylidene 2. We observed that while the reducing power of BI-s significantly decreases with increasing solvent polarity, the redox potential of the oxidant can increase at a greater rate, thus facilitating the reaction. The cation, associated with the base, also plays an important role when a nonpolar solvent is used; large and weakly coordinating cations such as Cs+ are beneficial. The radical-radical coupling step is probably the most challenging step due to both electronic and steric constraints. Based on our results, we predict that mesoionic carbene 3 and abnormal NHC 4 are the most promising candidates for oxidative carbene organocatalysis. © 2023 American Chemical Society.
URI
https://pr.ibs.re.kr/handle/8788114/13105
DOI
10.1021/acs.joc.2c02978
ISSN
0022-3263
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
Files in This Item:
There are no files associated with this item.

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse