Relative facility of the desulfurization of amino acids and their carboxylic derivatives. (5th May 2015)

• Record Type: Journal Article
• Authors: Sun, Xiao‐Hui; Yu, Hai‐Zhu; Yang, Meng‐Meng; Yang, Yi‐Meng; Dang, Zhi‐Min
• Is Part Of: Journal of physical organic chemistry. Volume 28:Number 9(2015:Sep.)
• Page Start: 586
• Page End: 590
• Publication Date: 2015-05-05
• Subjects: Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3453
• Languages: English
• ISSNs: 0894-3230

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>As an excellent alternative to native chemical ligations, the ligation–desulfurization strategy enables the ligations on the other N‐terminal peptides (in addition to Cys) and is highly promising in <named-content content-type="chemicalTechnology" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">peptide synthesis</named-content>. In the present study, the relative facility of the <named-content content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">desulfurization</named-content> on the pre‐sulfurized <named-content content-type="chemicalTechnology" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">amino acids</named-content> and their carboxylate derivatives has been examined with the aid of density functional theory calculations. It is found that the C–SH bond strengths of the sulfurized <named-content content-type="chemicalTechnology" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">amino acids</named-content> directly relate to the stability of the formed radical. By contrast, the <named-content content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">carboxylation</named-content> of the sulfurized <named-content content-type="chemicalTechnology" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">amino acids</named-content> greatly stabilizes the carbonyl radical center, and both the steric and electronic effects are important factors in determining the C–SH bond strength of the carboxylate precursors. Copyright © 2015 John Wiley & Sons, Ltd.</p> </abstract>