Carbon-Rich Trinuclear Octamethylferrocenophanes

Abstract

Several trinuclear ferrocenes are obtained by Friedel− Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1′-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl derivative (4a) by reaction with MeLi and AlCl 3 . The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl 3 to a [3]ferrocenophane with propene handle (6). Structure assignments are supported by X-ray crystallography and NMR spectroscopy, and mechanisms are proposed. Electrochemical behavior of the compounds was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of density functional theory calculations. The synthesized compounds and demonstrated transformations represent useful tools for preparation of materials for charge-transport studies in metal−molecule−metal junctions.

Thermo- and ROS-Responsive Self-Assembled Polymer Nanoparticle Tracers for 19F MRI Theranostics

“…Ferrocene carboxylic acid was prepared by ferrocene lithiation with Schlosser’s base according to ref .…”

Synthesis of Long-Chain Alkanoyl Benzenes by an Aluminum(III) Chloride-Catalyzed Destannylative Acylation Reaction

“…23 Furthermore, the blocking of carbon positions using unreactive methyl substituents allow acylations to be directed to certain available positions, as demonstrated for pentamethylbenzene, 24 tetramethylbenzene, 25 and octamethylferrocenes. 26,27 However, there are limited examples of the direct long-chain acylation of haloarenes, as the majority of studies are restricted to one substrate. The acylation of bromobenzene under Friedel−Crafts conditions has been reported; however, bromobenzene was used as solvent, and elevated temperatures (50 °C) were required.…”

“…Some halobenzoyl compounds have been prepared by the photochemical hydroacylation of olefins . Furthermore, the blocking of carbon positions using unreactive methyl substituents allow acylations to be directed to certain available positions, as demonstrated for pentamethylbenzene, tetramethylbenzene, and octamethylferrocenes. , …”

Asymmetric Friedel–Crafts Alkylation of Indoles Catalyzed by Chiral Aziridine-Phosphines

“…The enantioselective Friedel-Crafts reaction enables access to many valuable indole derivatives showing biological activity [18], like 2-and 3-substituted indoles [19], indoloquinolines [20] and spirooxindoles [21], and to the broad spectrum of other relevant molecules like dihydroisoquinolin-3-ones [22], (+)-aflatoxin B 2 [23], Dalesconol A and B [24], steroids [25], dihydrocoumarins [26] and trinuclear ferrocenes [27].…”