An efficient Pd/Cu bimetallic cross-coupling catalysis of fluoroaryl halides and fluoroarenes is reported. In situ generation of the Cu nucleophile by rate determining C–H activation of highly fluorinated aryls (≥...
Experimental kinetic studies and DFT calculations show that the oxidative addition of aryl halides (Ar–X) to complexes [Cu(NHC)R] follow different paths depending on the nature of X. For X =...
Neutral palladium(II) complexes [Pd(Rf)X(P-L)] (Rf = 3,5-C6Cl2F3, X = Cl, I, OTf) with P-P (dppe and dppf) and P-N (PPh2(bzN)) ligands have chelated structures in the solid-state, except for P-L...
19F NMR monitoring shows that heating trans-[AuIIIRf2I2]‒ solutions (Rf = C6F3Cl2-3,5) leads to formation of cis-[AuRf2I2]‒, [AuRf3I]‒ and [AuRfI3]‒ via kinetic competition between isomerization and Rf/I scrambling. The system evolution...
The synthesis of aryl−alkynyl compounds is usually achieved via Sonogashira catalysis, but this is inefficient for fluorinated aryls. An alternative method reported by Shirakawa and Hiyama, using alkynylstannanes and hemilabile PN ligands, works apparently fine for conventional aryls, but it is also poor for fluorinated aryls. The revision of the unusual literature cycle reveals the existence and nature of unreported byproducts and uncovers coexisting cycles and other aspects that explain the reasons for the conflict. This knowledge provides a full understanding of the real complexity of these aryl/alkynylstannane systems and the deviations of their evolution from that of a classic Stille process, providing the clues to design several very efficient alternatives for the catalytic synthesis of the desired Ar F −alkynyl compounds in almost quantitative yield. The same protocols are also very efficient for the catalytic synthesis of alkynyl−alkynyl' hetero-and homocoupling.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.