RESUMO
A series of ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands with varying degrees of backbone and N-aryl substitution have been prepared. These complexes show greater resistance to decomposition through C-H activation of the N-aryl group, resulting in increased catalyst lifetimes. This work has utilized robotic technology to examine the activity and stability of each catalyst in metathesis, providing insights into the relationship between ligand architecture and enhanced efficiency. The development of this robotic methodology has also shown that, under optimized conditions, catalyst loadings as low as 25 ppm can lead to 100% conversion in the ring-closing metathesis of diethyl diallylmalonate.
Assuntos
Alcenos/química , Metano/análogos & derivados , Rutênio/química , Alcenos/síntese química , Catálise , Ligantes , Malonatos/química , Metano/síntese química , Metano/químicaRESUMO
Conjugate acids of cyclic (amino)(phosphino)carbenes (P-NHCs) have been prepared, and several different processes have been observed during their deprotonation, which include the formation of a metastable P-NHC, an azomethine ylide, and a bicyclic phosphirane.
Assuntos
Alcinos/química , Dioxolanos/química , Compostos Heterocíclicos/síntese química , Compostos Organofosforados/síntese química , Fosfinas/química , Ácidos/química , Compostos Azo/síntese química , Compostos Azo/química , Cristalografia por Raios X , Compostos Heterocíclicos/química , Modelos Moleculares , Estrutura Molecular , Compostos Organofosforados/química , Tiossemicarbazonas/síntese química , Tiossemicarbazonas/químicaAssuntos
Alcenos/química , Aminas/síntese química , Iminas/síntese química , Ácidos/síntese química , Cristalografia por Raios X , Ciclização , Compostos Heterocíclicos/síntese química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Espectrometria de Massas de Bombardeamento Rápido de ÁtomosRESUMO
The presence of a second 1,3-diborata-2,4-diphosphoniocyclobutane-1,3-diyl in the para-position of a phenylene linker favors the diradical form over the 1,3-diborata-2,4-diphosphoniobicyclo[1.1.0]butane bond stretch isomer, as long as the two planar diradical units are coplanar with the linker. This demonstrates that two BPBP diradicals communicate through the phenyl ring.
RESUMO
Addition of a stoichiometric amount of HCl to alkenylaldimines, -formamidines, and -amidines results in the protonation of the sp2-nitrogen atom. The resulting alkenylaldiminium, -formamidinium, and -amidinium salts can be isolated and fully characterized, including single-crystal X-ray diffraction studies. Heating solutions of these salts induces ring closure cleanly and regioselectively via formal "exo" addition of the nitrogen-hydrogen bond to the pendent carbon-carbon double bond, affording the corresponding cyclic aldiminium, dihydroisoquinolinium, and imidazolinium salts. Of special interest, novel 4,4-disubstituted imidazolinium salts are accessible via this synthetic route. Similarly, addition of phosgene to alkenyl ureas and alkenyl amides, followed by gentle heating, cleanly affords C-chloro imidazolinium, and cyclic C-chloro iminium salts, respectively. Treatment of the latter with tetrakis(triphenylphosphine)palladium allows for the preparation of the first transition-metal complex bearing a cyclic arylaminocarbene as ligand. Deuterium labeling experiments suggest that the mechanism of the hydroiminiumation and -amidiniumation reactions involves an intramolecular proton transfer to the double bond in the rate-determining step. This novel synthetic methodology gives access to a variety of N-heterocyclic carbene (NHC) and cyclic alkyl- and arylaminocarbene (CAAC) precursors.