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The reactivity of a [V^V] alkylidyne with unsaturated substrates such as NCR (R = Ad or Ph) and PCAd leads to the formation of rare transition metal complexes featuring an α-aza-vanadacyclobutadiene and a β-phospha-vanadacyclobutadiene moieties. 

A pentadentate pyridinophane ligand is reported, along with a palladacycle product generatedviaCsp³–H bond activation under mild conditions. 

Photochemical electrocyclization reactions are valued for both their ability to produce structurally complex molecules and their central role in elucidating fundamental mechanistic principles of photochemistry. We present herein a highly enantioselective 6π photoelectrocyclization catalyzed by a chiral Ir(III) photosensitizer. This transformation was successfully realized by engineering a strong hydrogen-bonding interaction between a pyrazole moiety on the catalyst and a basic imidazolyl ketone on the substrate. To shed light on the origin of stereoinduction, we conducted a comprehensive investigation combining experimental and computational mechanistic studies. Results from density functional theory calculations underscore the crucial role played by the prochirality and the torquoselectivity in the electrocyclization process as well as the steric demand in the subsequent [1,4]-H shift step. Our findings not only offer valuable guidance for developing chiral photocatalysts but also serve as a significant reference for achieving high levels of enantioselectivity in the 6π photoelectrocyclization reaction. 

We show in this work how lithium tellurolate Li(X)_nTeCH₂SiMe₃(X = THF,n= 1, 1; X = 12-crown-4,n= 2, 2), can serve as an effective Te-atom transfer reagent to all group 5 transition metal halide precursors irrespective of their oxidation state.