ChemInform Abstract: ORGANOMETALLIC COMPOUNDS IN ORGANIC SYNTHESIS. PART 11. THE STRATEGY OF LATERAL CONTROL OF REACTIVITY: TRICARBONYLCYCLOHEXADIENEIRON COMPLEXES AND THEIR ORGANIC SYNTHETIC EQUIVALENTS

Abstract

Das Konzept von überlagerter lateraler Kontrolle ("superimposed lateral control") von Reaktivität, Stereochemie und Struktur durch Verknüpfung von komplexierten Metallatomen mit olefinischen Systemen wird entwickelt und diskutiert.

Azulene Functionalization by Iron-Mediated Addition to a Cyclohexadiene Scaffold

“…Such complexes are capable of reacting with a wide range of nucleophiles to form new carbon–carbon or carbon–heteroatom bonds . Nucleophilic addition proceeds in a highly selective manner at the opposite face to the iron carbonyl moiety and at one of the ends of the conjugated system. , Substituents on the cation can act to direct the nucleophilic addition to either termini of the dienyl system; electron-withdrawing groups will generally favor addition in the meta position, while electron-donating groups will often favor the para or ipso addition . The cationic complexes can be formed via hydride abstraction (Scheme , path a) or by acid treatment of a complex possessing a leaving group (Scheme , path b).…”

Selective Iron-Mediated C- and O-Addition of Phenolic Nucleophiles to a Cyclohexadiene Scaffold Using Renewable Precursors

“…The regioselectivity of the initial cation formation is governed by the substitution pattern of the diene. Subsequent nucleophilic addition then takes place stereoselectively, to the opposite face of the coordinated iron carbonyl moiety. , Other advantages of this methodology are the mild reaction conditions used, and the fact that the tailoring of reaction conditions for each class of nucleophile is generally not required. Applications of this method include the synthesis of natural products, such as siculinine and clausine K; antiviral compounds, such as oseltamivir phosphate (Tamiflu); , probes for infrared spectroscopy; as well as parallel synthesis applications .…”