Conjugated 1,5-diarylpent-2-en-4-yn-1-ones add the superacid CF3SO3H to the acetylenic bond with formation of the corresponding butadienyl triflates. Under superacidic reaction conditions, these triflates are transformed into indanone or indene derivatives depending on which substituents on the aromatic ring are conjugated with the butadiene fragment. In a less acidic system (10% vol pyridine in CF3SO3H) only the formation of butadienyl triflates takes place. Cationic reaction intermediates were studied by means of NMR and DFT calculations.

In triflic acid or sulfuric acid, diaryl‐substituted cross‐conjugated enynones undergo addition of the acid to the carbon–carbon triple bond to afford the corresponding vinyl triflates or sulfates. The vinyl triflates are stable under aqueous workup, whereas the vinyl sulfates are hydrolyzed to α,β‐unsaturated 1,3‐diketones (existing as conjugated enol forms). Extended reaction times lead to cyclization into dihydropyran‐4‐ones with yields of up to 95 %. The protonated forms of the vinyl triflates or sulfates in triflic and sulfuric acid, respectively, are studied as reactive intermediates by NMR spectroscopy. Plausible reaction mechanisms for the formation of dihydropyran‐4‐ones are discussed.

Under superelectrophilic activation in triflic acid (TfOH) and in the presence of arenes, 1,5-diarylpent-2-en-4-yn-1-ones lead to aryl-substituted indenes with yields up to 97%.

The combination of a practical and highly enantioselective organocatalytic reaction, which allows the stereoselective introduction of a benzodithiol group, with a fluorination step, gives a new and effective strategy for the stereoselective synthesis of difluorinated building blocks. The benzodithiol group is a versatile and chameleonic group that can be further functionalized before fluorination, giving customized and tailored useful synthetic strategies. As an example of the application of this facile strategy, the effective enantioselective synthesis of difluoroarundic acid is described.

Recently, the direct substitution of allylic, benzylic, and tertiary alcohols has been achieved via SN 1-type reactions with catalytic amounts of Brønsted or Lewis acids. When a new stereogenic center is formed most of these transformations produce the desired product as a racemate, as these reactions proceed through carbenium ions. The arsenal of activation modes available in organocatalysis can be used to set up suitable reaction conditions in which chiral nucleophiles (enamine catalysis) or chiral electrophiles (iminium catalysis, chiral counterion catalysis) can easily be generated. Recently, we have used stabilized carbenium ions, directly available or obtained from the corresponding alcohols, in new organocatalytic stereoselective SN 1-type reactions. The commercially available carbenium ion benzodithiolylium tetrafluoroborate can be used for the straightforward organocatalytic stereoselective alkylation of aldehydes. In this account we will illustrate the application of this methodology in the total synthesis of natural products and the preparation of valuable starting materials.