Multicomponent reactions are fundamentally different from two-component reactions, as multicomponent reactions can enable the efficient and step-economical construction of complex molecular scaffolds from simple precursors. Here, an unprecedented threecomponent direct C−H addition was achieved in the challenging meta-selective fashion. Fluoroalkyl halides and a wide range of alkenes, including vinylarenes, unactivated alkenes, and internal alkenes, were employed as the coupling partners of arenes in this strategy. The detailed mechanism presented is supported by kinetic isotope studies, radical clock experiments, and density functional theory calculations. Moreover, this strategy provided access to various fluoride-containing bioactive 1,1diarylalkanes and other challenging synthetically potential products.
Highly functionalized 4-aminoindoles
were synthesized via the three-component
cross-coupling of o-iodoaniline, N-benzoyloxyamines, and norbornadiene. The Catellani and retro-Diels–Alder
strategy was used in this domino process. o-Iodoaniline,
with electron-donating and sterically hindered protecting groups,
made the reaction selective toward o-C–H amination.
On the basis of density functional theory calculations, the intramolecular
Buchwald coupling of this reaction underwent a dearomatization and
a 1,3-palladium migration process. The reasons for the control of
the chemical selectivity by the protecting groups are given. Moreover,
synthetic applications toward 4-piperazinylindole and a GOT1 inhibitor
were realized.
Photo-induced radical reductive dehalogenation of inactivated aryl/alkyl bromides and chlorides with a palladium complex is described. Reductive cyclization, dehalogenative deuteration, and radical addition process can be achieved smoothly.
Free radical cyclization has emerged as one of the most important reaction types, which is widely used in natural product synthesis, pharmaceutical chemistry, and materials science. This report described the combination of radical cyclization and ruthenium-catalyzed meta-selective C−H functionalization for the synthesis of arylpyrrolidone derivatives. This method exhibited the highly meta-site selectivity of the primary, secondary, and tertiary alkyl radicals formed by intramolecular addition. A wide spectrum of directing groups bearing diversified N-heterocycles performed well, including biologically active molecules. Density functional theory calculations provided a theoretical basis for the high metaselectivity and the favored reaction pathway of an intramolecular cyclization.
This report describes palladium catalyzed C-H glycosylation and retro Diels-Alder tandem reaction via structurally modified norbornadiene (smNBDs). The smNBDs was proposed to regulate the reactivity of aryl-norbornadiene-palladacycle (ANP) process, as...
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.