Mechanistic study on the Knorr pyrazole synthesis-thioester generation reaction |
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| Authors: | Yijun Du Yanyan Xu Chenze Qi Chen Wang |
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| Affiliation: | 1. Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, Shaoxing University, Shaoxing 312000, People’s Republic of China;2. Yuanpei College, Shaoxing University, Shaoxing 312000, People’s Republic of China |
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| Abstract: | A novel Fmoc-SPPS compatible peptide thioester generation method leveraging Knorr pyrazole synthesis was reported recently. C-terminal peptide hydrazides, pentane-2,4-dione and excess arylthiol were added in one-pot to efficiently produce peptide thioesters in acidic aqueous solution at room temperature. To elucidate the detailed mechanism of this reaction and the origin of the effect of solution acidity, a theoretical investigation on the Knorr pyrazole synthesis-thioester generation reaction was carried out. Our computational results suggest that the reaction generally proceeds through three stages: hydrazone formation, pyrazole formation and thioester formation. The rate-determining step is the C | |
| Keywords: | Corresponding author. Knorr pyrazole synthesis Thioester Native chemical ligation Mechanism Theoretical calculations |
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