RESUMO
Employing a low loading of the terminal oxidant, a remote directing group-enabled radical relay strategy for benzylic direct C(sp3)-H alkoxylation with alcohols at room temperature is developed. Satisfactory site-selectivity, chemoselectivity, and reaction scope are achieved under simple and mild conditions, and no ligand or additive is required. Mechanistic studies, ready conversions of the directing group, and other benzylic functionalizations currently under development in our laboratory further indicate the promising potentials of this remote directing group-enabled radical relay strategy.
Assuntos
Etanol , Benzeno/química , Catálise , TemperaturaRESUMO
Employing N-fluorobenzenesulfonimide (NFSI) as a nitrogen-centered radical (NCR) precursor, an intermolecular C(sp2)-N coupling on heteroarenes or substituted benzenes with remote activated aniline derivatives via copper catalyzed N-N radical relay strategy at room temperature is developed. Good to excellent yields are acquired, and no ligand or additive is required. Reaction scope investigation and preliminary mechanistic studies demonstrate that the remote activating strategy and delicate control on the reactivities of active NCR species are essential to guarantee satisfactory chemo- and site-selectivity.
RESUMO
Direct C5-alkylation of oxazole/thiazole with ether or cycloalkane has been achieved through a cobalt-catalyzed cross-dehydrogenative coupling (CDC) process in moderate to good yields. This transformation represents the first C(sp2 )-C(sp3 ) cross-coupling at the C5-position of the oxazole/thiazole via double C-H bond cleavages. Various functional groups on oxazole/thiazole substrates, as well as water and air, are well-tolerated with this concise and practical protocol, constituting straightforward access to heterocycles with great medicinal significance. A preliminary mechanism involving a radical process has also been proposed.