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6601198 
Journal Article 
Asymmetric hydrosilylation of olefins catalyzed by MOP-palladium complexes 
Hayashi, T; , 
1996 
Yes 
Acta Chemica Scandinavica
ISSN: 0904-213X
EISSN: 1902-3103 
MUNKSGAARD INT PUBL LTD 
COPENHAGEN 
50 
259-266 
English 
Axially chiral monophosphines, 2-(diphenylphosphino)-2'-methoxy-1,1'-binaphthyl (MeO-MOP, 1a) and its biphenanthryl analog 5, were prepared starting with homochiral 2,2'-dihydroxy-1,1'-binaphthyl and 3,3'-dihydroxy-4,4'-biphenanthryl, respectively. The palladium complexes coordinated with the MOP ligands are highly effective catalysts for several types of catalytic asymmetric reaction where chelating bisphosphine ligands cannot be used because of their low catalytic activity or low selectivity towards the desired reaction pathway. Palladium-catalyzed hydrosilylation of olefins is one of the typical examples. High enantioselectivity was observed in the asymmetric hydrosilylation of alkyl-substituted terminal olefins (92-97% ee), bicyclo[2.2.1]heptene derivatives (92-96% ee), styrene derivatives (89-96% ee), and cyclic 1,3-dienes (80% ee). The hydrosilylation products were efficiently converted into optically active alcohols by oxidation of the carbon-silicon bond. 
Nobel Symposium on Catalytic Asymmetric Synthesis 
TAMMSVIK, SWEDEN