Anew concept for selectivity control in carbocationdriven reactions has been identified which allows for the chemo-, regio-, and stereoselective addition of nucleophiles to alkynes-assisted vinyl cation formation-enabled by aL i +based supramolecular framework. Mechanistic analysis of am odel complex (Li 2 NTf 2 + ·3 H 2 O) confirms that solely the formation of acomplex between the incoming nucleophile and the transition state of the alkyne protonation is responsible for the resulting selective Naddition to the vinyl cation. Into the bargain, ageneral, operationally simple synthetic procedure to previously inaccessible vinyl triflimides is provided.

The first transition metal-free cycloisomerization of easily accessible diynols is presented as a novel approach to bicyclic 2H-pyrans. As a one-step protocol, the reaction proceeds in a single reaction cascade by intertwining mechanistic fragments borrowed from transition metal-catalyzed Claisen rearrangment of vinyl ethers with our own work on allenyl/propargyl cation rearrangements and a 6π-oxo-electrocylization. It is enabled by a new cooperative catalytic system that combines a simple Ca(2+) catalyst with camphorsulfonic acid.

Abracadabra! Homolytic bond cleavage enabled by visible‐light‐induced triplet–triplet energy transfer makes us think of a thioxanthone wizard who performs her magic when being excited in the spotlight. She transfers the energy with her wand to the vinyl triflimides thus inducing homolytic N−S bond cleavage to reveal radicals. Just like the divided woman, these recombine leading to α‐quaternary‐β‐trifluoromethylated amines. More information can be found in the Research Article by M. Niggemann and co‐workers (DOI: 10.1002/chem.202201830).

Vinyl triflimides are a new compound class with unknown reactivity. A computational analysis identified homolytic cleavage of the N−Tf bond induced by triplet–triplet energy transfer (EnT) as a highly interesting reaction type that might be accessible. A combination of experimental and mechanistic work verified this hypothesis and proved the generated radicals to be amenable to radical–radical coupling. Thereby, vinyl triflimides were transformed into a range of α‐quaternary, β‐trifluoromethylated amines in a 1,2‐difunctionalization reaction with no need for external CF3 reagents.

The Alkynyl Moiety as a Donor for Donor-Acceptor Cyclopropanes. -A calcium-catalyzed [3 + 2]-cycloaddition of aldehydes with a new type of quaternary donor site cyclopropanes, bearing an alkyne moiety as the sole donor entity, is presented. The method provides an unprecedented general access to highly substituted tetrahydrofurans bearing an alkyne moiety with excellent diastereoselectivities. -(HAUBENREISSER, S.; HENSENNE, P.; SCHROEDER, S.; NIGGEMANN*, M.; Org. Lett. 15 (2013) 9, 2262-2265, http://dx.