Allyl‐Palladium‐Catalyzed α,β‐Dehydrogenation of Carboxylic Acids via Enediolates

A highly practical and step‐economic α,β‐dehydrogenation of carboxylic acids via enediolates is reported through the use of allyl‐palladium catalysis. Dianions underwent smooth dehydrogenation when generated using Zn(TMP)₂⋅2 LiCl as a base in the presence of excess ZnCl₂, thus avoiding the typical decarboxylation pathway of these substrates. Direct access to 2‐enoic acids allows derivatization by numerous approaches.     

Chemical Bonding in Polarised Push–Pull Ethylenes

1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). In the twisted compound, a dominant contribution of the charge‐separated resonance structure was revealed. On the contrary, the nearly planar compound still showed π‐bonding character, however, with a considerable contribution of the charge‐separated resonance structure.     

A 3D Analogue of Phenyllithium: Solution‐Phase,Solid‐State,and Computational Study of the Lithiacarborane [Li−CB11H11]−

The lithiacarborane [Li?CB₁₁H₁₁]^? plays a central role in carborane chemistry, as it is a key intermediate to achieve the selective functionalization of the monocarba‐closo‐dodecaborate [CB₁₁H₁₂]^? for applications in various fields. Also, it is an organometallic species of fundamental interest because it represents a 3D analogue of phenyllithium featuring an exo C?Li bond in addition to the delocalized negative endo charge of the spherical cluster. For the first time, the elusive and highly reactive endo/exo formal dianion [CB₁₁H₁₁]^2? has been isolated as its lithiate as well as zincate in pure form and fully characterized. DFT calculations corroborate the experimental findings and underscore the remarkably high reactivity of the lithiacarborane. Subsequent derivatizations demonstrate the relevance of its initial clean formation.