Citation: Xiao-Hui Sun, Hai-Zhu Yu, Shu-Qi Pei, Zhi-Min Dang. Theoretical investigations on the thiol-thioester exchange steps of different thioesters[J]. Chinese Chemical Letters, ;2015, 26(10): 1259-1264. doi: 10.1016/j.cclet.2015.07.003 shu

Theoretical investigations on the thiol-thioester exchange steps of different thioesters

Xiao-Hui Sun ^1,2 ,
Hai-Zhu Yu ^2,, ,
Shu-Qi Pei ¹ ,
Zhi-Min Dang ^1,,

1.
1 Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China;
2.
2 Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui University, Hefei 230601, China

Corresponding author: Hai-Zhu Yu, Zhi-Min Dang,
Received Date: 9 April 2015
Available Online: 10 June 2015
Fund Project: We appreciate NSFC (No. 21202006) (No. 21202006)FRFCU (No. FRF-TP- 14-015A2) for financial supports and Super-computer Center of Shanghai and Shenzhen for technical supports. (No. FRF-TP- 14-015A2)

As the rate-determining step in native chemical ligation reactions, the thiol-thioester exchange step is important in determining the efficiency of the ligations of peptides. In the present study, systematic theoretical calculations were carried out on the relationships between the structure of different thioesters and the free energy barriers of the thiol-thioester exchange step. According to the calculation results, the thiol-thioester exchange step is disfavored by the steric hindrance around the carbonyl center, while the electronic effect (i.e. conjugation and hyper-conjugation effects) becomes important when the steric hindrance is insignificant.
- Native chemical ligation,
- Thiol-thioester exchange,
- Density functional theory
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