Unexpected Pd-Catalysed Substitution on the Triquinanedione System - An Approach to centro-Substituted Triquinanes

Three-Dimensional Hydrocarbon Cores Based on Multiply Fused Cyclopentane and Indane Units: Centropolyindanes

“…Numerous efforts were invested to pursue this idea, including an approach by multiple aldol addition of the C 3 -symmetrical, and thus chiral, perhydroquinacenetrione 21 by Serratosa et al . Besides the discussion on the long-assumed homoconjugative interaction between the π bonds of 18 , − the generation and properties of the triquinacene-10-yl cation was put forward. ,, Many bridgehead-functionalized derivatives of triquinacene, such as 19 , − a few centro -substituted ones, e.g., 20 , , and peripherally functionalized ones, e.g., the interesting all- exo -hexaol 22 , have been described and studied, mainly with respect to their reactivity toward complexation with metal carbonyl fragments, reduction, and elimination. The deprotonation/dehydrogenation pathways of 18 and some derivatives by use of superbases have also been studied in great detail, ,− and the existence of neutral acepentalene ( 23 ), having remained elusive in condensed media, was demonstrated in the gas phase .…”

Catalytic β-Functionalization of Carbonyl Compounds Enabled by α,β-Desaturation

“…Other cyclic and linear ketones beyond cyclohexanones could also be smoothly arylated. It should be noted that, during one control experiment of the aforementioned β′-arylation of β-keto esters with electron-rich arene nucleophiles, Pihko and co-workers also observed the β-arylation product using iodobenzene. , …”

Catalytic applications of transition metals in organic synthesis

“…Uenishi and co-workers have reported a selective De Meijere and co-workers have reported the unexpected formation of the centro-substituted triquinane 127 in the coupling of diketone 128 and iodobenzene 129 (Scheme 42). 82 The reaction may proceed via oxidation to an a,P-unsaturated diketone, followed by a reductive Heck hydroarylation. The zirconium catalysed enantioselective methylalumination of monosubstituted alkenes has been described by Kondakov and Negi~hi.…”