Carbon dioxide enhances sulphur-selective conjugate addition reactions

Abstract

Sulphur-selective conjugate addition reactions play a central role in synthetic chemistry and chemical biology. A general tool for conjugate addition reactions should provide high selectivity in the presence of competing...

Taming diamines and acyl chlorides by carbon dioxide in selective mono-acylation reactions

“…[24][25][26][27][28] Recently, our group have also showed an application of CO 2 in sulfur-selective Michael addition reac-tions of cysteine residues on peptides and proteins, which contain competing lysine residues. 29 Based on these precedents, we envisaged that the interactions between the nitrogen nucleophiles of diamines and CO 2 could be harnessed to favour a desired reaction pathway over the other. Herein, we demonstrate the use of CO 2 in controlling the reactivity of diamine nucleophiles.…”

“…24–28 Recently, our group have also showed an application of CO 2 in sulfur-selective Michael addition reactions of cysteine residues on peptides and proteins, which contain competing lysine residues. 29…”

Translation of a Phosphine- and Azide-Based Reaction to Chemical Modification of Biomolecules in Ionic Liquid

“…37 38 Taking into account the previously proposed reaction mechanisms for small-molecule substrates, 39 40 41 we propose that the bioconjugation reaction proceeds through a reactive isocyanate intermediate, which is known to be an excellent alkylamine-selective modification of biomolecules (Scheme 4 B). 42 Reactions of CO 2 and amine-forming carbamic acid 43 44 are also known processes even in ionic liquids, 45 although, to our knowledge, formation of urea from carbamic acid and iminophosphorane has not been reported.…”