Synthesis of lanthanide(II)–imine complexes and their use in carbon–carbon and carbon–nitrogen unsaturated bond transformation
作者:Ken Takaki、Kimihiro Komeyama、Katsuomi Takehira
DOI:10.1016/j.tet.2003.06.003
日期:2003.12
1 quantitatively, the structure of which was characterized by X-ray analysis. The imine complexes 1 catalyzed dehydrogenativesilylation of terminal alkynes, hydrosilylation of imines and alkenes, and intermolecular hydrophosphination of alkynes. Moreover, dehydrogenative double silylation of conjugated dienes was achieved with 1.
Divalent lanthanide–imine complexes and a related species catalyzed the hydrosilylation of olefins with phenyl- and diphenylsilane. On the other hand, conjugated dienes were converted to 1,4-bissilyl-2-butenes and 3-silacyclopentenes, accompanied with hydrogen evolution, under similar conditions.
Magnesium hydride alkene insertion and catalytic hydrosilylation
作者:Lucia Garcia、Chiara Dinoi、Mary F. Mahon、Laurent Maron、Michael S. Hill
DOI:10.1039/c9sc02056j
日期:——
mol-1. This Mg-H/C[double bond, length as m-dash]C insertion reactivity provides the basis for the catalytichydrosilylation of terminal alkenes with PhSiH3, which proceeds with a preference for the formation of the anti-Markovnikov organosilane product. Further DFT calculations reveal that the catalytic reaction is predicated on a sequence of Mg-H/C[double bond, length as m-dash]C insertion and classical
set of base metal catalysts has been developed for regiodivergent alkene hydrosilylations: iron complexes of phosphine‐iminopyridine are selective for anti‐Markovnikov hydrosilylations (linear/branched up to >99:1), while the cobalt complexes bearing the same type of ligands provide an unprecedented high level of Markovnikov selectivity (branched/linear up to >99:1). Both systems exhibit high efficiency