Cationic Dieckmann condensation

Some straightforward, efficient cyclopentanellation procedures were developed recently. Addition of a malonic ester anion to a cyclopropane-1,1-dicarboxylic ester followed by a Dieckmann condensation (S. Danishefsky, 1974) or addition of iJ-ketoester anions to a (l-phenylthiocyclopropyl)phosphonium cation followed by intramolecular Wittig reaction (J.P, Marino. 1975) produced cyclopentanones. Another procedure starts with a (2 + 21-cycloaddition of dichloroketene to alkenes followed by regioselective ring expansion with diazomethane. The resulting 2,2-dichlorocyclopentanones can be converted to a large variety of cyclopentane derivatives (A.E. Greene. 1979 J.-P. Deprds, 1980). 

In the first and asymmetric total synthesis of rubriflordilactone A shown below, the advanced intermediate furofuranone was constructed through an intramolecular Dieckmann condensation followed by a cationic deoxygenation reaction (14JA16477). 

Thermal degradation led to the oxo compounds including [(N02)N0)][Ti0(F3CS03)4], Tilv triflate complexes efFiciently catalyze a variety of reactions including the conversion of acetophenones to 1,3,5-triarylbenzenes,658 the nucleophilic ring opening of epoxides,659 Diels—Alder reactions,660 selective Claisen and Dieckmann ester condensations,661 esterification reactions,662 Fries rearrangements,663 homoaldol reactions,664 sequential cationic and anionic polymerizations,641 and the stereoselective synthesis of m-arabinofuranosides.606... 

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