Modification of Chiral Monodentate Phosphine Ligands (MOP) for Palladium-Catalyzed Asymmetric Hydrosilylation of Cyclic 1,3-Dienes

• Published in: Advanced synthesis & catalysis Vol. 343; no. 3; pp. 279 - 283
• Main Authors: Hayashi, Tamio, Han, Jin Wook, Takeda, Akira, Tang, Takeda, Nohmi, Kenji, Mukaide, Kotaro, Tsuji, Hayato, Uozumi, Yasuhiro
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley-VCH Verlag GmbH 30.03.2001; Wiley‐VCH Verlag GmbH
• Subjects: allylsilane; asymmetric catalysis; chiral monodentate phosphine ligands; hydrosilylations; palladium
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/1615-4169(20010330)343:3<279::AID-ADSC279>3.0.CO;2-5

Several MOP ligands 5 containing aryl groups at 2′ position of (R)‐2‐(diphenylphosphino)‐1,1′‐binaphthyl skeleton were prepared and used for palladium‐catalyzed asymmetric hydrosilylation of cyclic 1,3‐dienes 6 with trichlorosilane. Highest enantioselectivity was observed in the reaction of 1,3‐cyclopentadiene (6a) catalyzed by a palladium complex (0.25 mol %) coordinated with (R)‐2‐(diphenylphosphino)‐2′‐(3,5‐dimethyl‐4‐methoxyphenyl)‐1,1′‐binaphthyl (5f), which gave (S)‐3‐(trichlorosilyl)cyclopentene of 90% ee.