RESUMEN
Site-selective C-H fluorination is an attractive strategy for directly transforming inert C-H bonds into C-F bonds, yet it remains a significant challenge. Herein, we have developed an efficient and versatile strategy for site-selective fluorination and amination of phenylalanine-containing peptides via late-stage Pd-catalyzed δ-C(sp2)-H activation, providing a valuable tool for the in situ synthesis of fluorinated indoline scaffolds within peptides.
Asunto(s)
Halogenación , Paladio , Estructura Molecular , Paladio/química , Aminación , Catálisis , PéptidosRESUMEN
An efficient and straightforward strategy to synthesize imidazo[1,5-a]pyridine compounds from phenylalanine and halohydrocarbon has been successfully developed. The protocol features a relay copper-catalyzed reaction involving intermolecular C-O coupling and intramolecular C-N cyclization, providing an approach to access a diverse range of imidazo[1,5-a]pyridine derivatives with unique aza quaternary carbon centers.
RESUMEN
Efficient synthesis of phenylalanine-derived oxazoles and imidazolidones can be achieved by copper-catalyzed reactions that are controlled by directing groups and proceed by selective C-O or C-N coupling. This strategy employs inexpensive commercial copper catalysts and readily available starting materials. It uses a convenient reaction procedure and provides a reliable approach to the versatile and flexible assembly of heterocyclic building blocks.
RESUMEN
An efficient and concise strategy for the synthesis of cyclic dipeptides via Pd-catalyzed site-selective δ-C(sp2)-H amination/fluorination and N-to-C cyclization is disclosed. The backbone amides within the dipeptides serves as endogenous directing groups, while the desired products were switched by the C-terminal ester group. This chemistry presents a novel and robust alternative to construct cyclodipeptide fragments.
RESUMEN
We present a method for site-selective diversification of peptides via Pd-catalyzed ß-C(sp3)-H olefination/cyclization. In this protocol, the native methionine residue acts as a directing group, enabling site-specific olefination/cyclization of peptides. This chemistry demonstrates broad substrate scope, offering a versatile tool for peptide ligation.
Asunto(s)
Alquenos , Metionina , Paladio , Péptidos , Catálisis , Paladio/química , Alquenos/química , Metionina/química , Ciclización , Péptidos/química , Estructura MolecularRESUMEN
Backbone-enabled site-selective modification of peptides with benzoquinone via Pd-catalyzed δ-C(sp2)-H functionalization has been achieved. The amide groups of peptides serve as internal directional groups, facilitating C-H functionalization through a kinetically less favored six-membered palladacycle. This methodology presents novel opportunities for the late-stage site-selective diversification of peptides.
RESUMEN
An efficient and straightforward approach for site-selective functionalization of phenylalanine and phenylalanine-containing peptide via a Pd-catalyzed tandem reaction has been developed. The robust method underwent dual C-H activation, including C-C coupling with benzoquinone and intramolecular C-N cyclization, providing a feasible and rapid synthetic route to incorporate 4-benzoquinone-indoline fragments into peptides.