Journal
SCIENCE CHINA-CHEMISTRY
Volume 55, Issue 10, Pages 2075-2080Publisher
SCIENCE PRESS
DOI: 10.1007/s11426-012-4711-x
Keywords
density functional theory; native chemical ligation; thioester; O-to-S acyl transfer; hydrolysis
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Funding
- National Natural Science Foundation of China [20932006]
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Peptide thioester preparation via intramolecular O-to-S acyl transfer is a recently developed method for protein chemical synthesis through Fmoc chemistry. Theoretical calculations have been carried out to study the mechanism for the formation of thioesters via O-to-S acyl transfer. It is found that the O-to-S acyl transfer occurs via an anionic stepwise mechanism in which the cleavage of the C-O bond is the rate-limiting step. The side reaction of hydrolysis also proceeds through an anionic stepwise process, and its rate-limiting step is the attack of the hydroxide ion on the carbonyl carbon. Increase of the chain length between the ester O atom and the S atom can increase the energy barrier of the O-to-S acyl transfer. On the other hand, substituents at the alpha-position of the ester can reduce the energy barrier.
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