化学
硅氢加成
烷基
螯合作用
磷
立体化学
手性(物理)
药物化学
对映选择合成
小学(天文学)
方位(导航)
有机化学
催化作用
手征对称性
物理
地图学
天文
地理
量子力学
Nambu–Jona Lasinio模型
夸克
作者
Ryoichi Kuwano,Masaya Sawamura,Junya Shirai,Masatoshi Takahashi,Yoshihiko Ito
摘要
Abstract Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)-secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.
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