An Umpolung Approach for the Chemoselective Arylation of Selenocysteine in Unprotected Peptides
نویسندگان
چکیده
Herein we report an umpolung strategy for the bioconjugation of selenocysteine in unprotected peptides. This mild and operationally simple approach takes advantage of the electrophilic character of an oxidized selenocysteine (Se-S bond) to react with a nucleophilic arylboronic acid to provide the arylated selenocysteine within hours. This reaction is amenable to a wide range of boronic acids with different biorelevant functional groups and is unique to selenocysteine. Experimental evidence indicates that under oxidative conditions the arylated derivatives are more stable than the corresponding alkylated selenocysteine.
منابع مشابه
Chemoselective Intermolecular Cross-Enolate-Type Coupling of Amides
A new approach for the synthesis of 1,4-dicarbonyl compounds is reported. Chemoselective activation of amide carbonyl functionality and subsequent umpolung via N-oxide addition generates an electrophilic enolonium species that can be coupled with a wide range of nucleophilic enolates. The method conveys broad functional group tolerance on both components, does not suffer from formation of homoc...
متن کاملCatalyst-controlled chemoselective arylation of 2-aminobenzimidazoles.
The chemoselective and complementary Pd-and Cu-catalyzed N-arylation of 2aminobenzimidazoles is described. Selective N-arylation of the amino-group was achieved with a Pd-catalyzed method, while selective N-arylation of azole nitrogen was achieved with a Cucatalyzed procedure. The utility of these complementary sets of conditions is demonstrated in several two-step, selective syntheses of di-ar...
متن کاملOrthogonal ligation strategies for peptide and protein.
This review focuses on the concept, criteria, and methods of an orthogonal amide ligating strategy suitable for syntheses of peptides, peptide mimetics, and proteins. Utilizing unprotected peptides or proteins derived from chemical or biosynthetic sources, this ligation strategy has been shown to be general and exceptionally mild. Its orthogonality in ligating two unprotected segments with free...
متن کاملChemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides
In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach...
متن کاملChemoselective Palladium-Catalyzed Deprotonative Arylation/[1,2]-Wittig Rearrangement of Pyridylmethyl Ethers.
Control of chemoselectivity is one of the most challenging problems facing chemists and is particularly important in the synthesis of bioactive compounds and medications. Herein, the first highly chemoselective tandem C(sp3)-H arylation/[1,2]-Wittig rearrangement of pyridylmethyl ethers is presented. The efficient and operationally simple protocols enable generation of either arylation products...
متن کامل