Dehydrogenative silylation of primary and secondary amines with triphenylsilane was catalyzed by ytterbium-imine complexes, [Yb(eta(2)-Ph2CNAr)(hmpa)(n)], to give aminosilanes in good yields. In the reaction with diphenyl- and phenylsilanes, diaminosilanes were formed as major products. Whereas n- and sec-alkylamines were readily silylated, tert-alkylamines and aromatic amines exhibited lower reactivities. Moreover, hydrosilylation of imines has been achieved by using phenylsilane and the imine complexes (Ar = Ph, C6H4F-4), giving rise to mono- and diaminosilanes. The two reactions were in agreement as regards the product selectivities and yields.
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.