RESUMEN
In this report, we demonstrate olefin transposition/isomerization reactions catalyzed by a series of N,N,N-pincer (1,3-bis(2-pyridylimino)isoindoline) Ru-hydride complexes. The protocol proceeds at room temperature for most substrates, achieving excellent yields, regioselectivity, and diastereoselectivity in short reaction times. The air-stable Ru-chloride derivatives of these complexes exhibit comparable reactivity enabling benchtop setup and synthetic versatility. Furthermore, we demonstrate the potential for one-pot cascade sequences of the products derived from the transposition reactions.
RESUMEN
A photoredox/cobalt dual catalytic procedure has been developed that allows benzoylation of olefins. Here the photoredox catalyst effects the decarboxylation of α-ketoacids to form benzoyl radicals. After addition of this radical to styrenes, the cobalt catalyst abstracts a H-atom. Hydrogen evolution from the putative cobalt hydride intermediate allows a Heck-like aroylation without the need for a stoichiometric oxidant. Mechanistic studies reveal that electronically different styrenes lead to a curved Hammett plot, thus suggesting a change in product-determining step in the catalytic mechanism.
Asunto(s)
Alquenos , Cetoácidos , Cobalto , Catálisis , EstirenosRESUMEN
Invited for the cover of this issue is the group of Jon Tunge at the University of Kansas. The image depicts the direct cross-coupling of α-oxo acids and styrenes through the release of CO2 and H2 gas in a metallaphotoredox process. Read the full text of the article at 10.1002/chem.202202781.
RESUMEN
A photocatalytic methodology for the single step synthesis of γ-ketoacids from α-ketoacids has been developed. This method employs maleic anhydrides as traceless synthetic equivalents of acrylic acids, achieving a selective cross-coupling via a dual decarboxylative strategy, where molecular CO2 is released as the only waste byproduct. The method has also been expanded to incorporate a highly regioselective, 3-component coupling with various alcohols to access functionalized γ-ketoesters.