Novel Chiral Ligands, Diferrocenyl Dichalcogenides and Their Derivatives, for Rhodium- and Iridium-Catalyzed Asymmetric Hydrosilylation

摘要: As chiral ligands for transition metal complex-catalyzed asymmetric reactions, a variety of novel ferrocenyl chalcogen compounds, which possess planar chirality due to the 1,2-unsymmetrically disubstituted ferrocene structure, have been prepared from ferrocenes. There are seven diferrocenyl dichalcogenides (4−10), nine alkyl or aryl chalcogenides (11−19), two bis(ferrocenylseleno)alkanes (20 and 21), 1-(phenylchalcogeno)-1-[2-(diphenylphosphino)ferrocenyl]ethanes (22 24), 1-(phenylchalcogeno)-1-[1‘,2-bis(diphenylphosphino)ferrocenyl]ethanes (23 25). 2,3-O,O‘-Isopropylidene-2,3-dihydroxy-1,4-bis(phenylchalcogeno)butanes (26−28) also synthesized. The Rh(I) hydrosilylation ketones with diphenylsilane in presence these including reported [R,S;R,S]-bis[2-[1-(dimethylamino)ethyl]ferrocenyl] (1−3), followed by hydrolysis dilute HCl, affords corresponding alcohols (R-configuration) mo...