TY - JOUR
T1 - Thio-conjugation of substituted benzofurazans to peptides
T2 - molecular sieves catalyze nucleophilic attack on unsaturated fused rings
AU - Verdoliva, Valentina
AU - Digilio, Giuseppe
AU - Saviano, Michele
AU - De Luca, Stefania
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2020.
PY - 2021/2/7
Y1 - 2021/2/7
N2 - Bioconjugates of 2,1,3-benzoxadiazole (benzofurazan) and its derivatives have attracted considerable interest due to their biological activities and applications as fluorescent tags. A high-yield, chemoselective, and mild procedure for theS-alkylation of cysteine containing peptides by benzofurazan halogenides is reported. The key feature of this procedure is the use of activated molecular sieves (MS) to catalyze thiol activation for nucleophilic substitution under very mild conditions (room temperature and no need for added bases). To the best of our knowledge, this is the first report about thiol nucleophilic substitution performed on unsaturated and annelated systems catalyzed by activated molecular sieves. Reaction yields were remarkable even with benzofurazans having weakly activating groups or no activating groups at all. The potential of the new methodology was explored by synthesizing fluorescent, hydrophilic benzofurazan/peptide conjugates, also with peptides containing unprotected lysine residues.
AB - Bioconjugates of 2,1,3-benzoxadiazole (benzofurazan) and its derivatives have attracted considerable interest due to their biological activities and applications as fluorescent tags. A high-yield, chemoselective, and mild procedure for theS-alkylation of cysteine containing peptides by benzofurazan halogenides is reported. The key feature of this procedure is the use of activated molecular sieves (MS) to catalyze thiol activation for nucleophilic substitution under very mild conditions (room temperature and no need for added bases). To the best of our knowledge, this is the first report about thiol nucleophilic substitution performed on unsaturated and annelated systems catalyzed by activated molecular sieves. Reaction yields were remarkable even with benzofurazans having weakly activating groups or no activating groups at all. The potential of the new methodology was explored by synthesizing fluorescent, hydrophilic benzofurazan/peptide conjugates, also with peptides containing unprotected lysine residues.
UR - http://www.scopus.com/inward/record.url?scp=85101173009&partnerID=8YFLogxK
U2 - 10.1039/d0cy02004d
DO - 10.1039/d0cy02004d
M3 - Article
SN - 2044-4753
VL - 11
SP - 1067
EP - 1076
JO - Catalysis Science and Technology
JF - Catalysis Science and Technology
IS - 3
ER -