Palladium-catalyzed 1, 4-disylation of α, β-unsaturated ketones with 1, 1-dichloro-1-phenyl-2,2,2-trimethyldisilane

✍ Scribed by Tamio Hayashi; Yonetatsu Matsumoto; Yoshihiko Ito

• Book ID: 104216590
• Publisher: Elsevier Science
• Year: 1988
• Tongue: French
• Weight: 272 KB
• Volume: 29
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)80440-2

✦ Synopsis

1,4_Disilylation of a,@-unsaturated ketones proceeded with l,l-dichloro-l-phenyl-2,2,2_trimethyldisilane in the presence of a phosphine-palladium catalyst in benzene. Treatment of the disilylation products with an excess of methyllithium generated b-silyl lithium enolates, of which hydrolysis and alkylation gave g-(phenyldimethylsilyl) ketones and anti Bsilyl a-alkyl ketones, respectively.

Fleming and coworkers have reported1 that conjugate addition of a silyl group to a,Bunsaturated carbonyl compounds is effected by use of a silyl cuprate reagent and the resulting B-silyl carbonyl compounds are useful synthetic intermediates convertible, for example, into E-hydroxy ketones. Here we wish to describe a new conjugate silylation of a,&unsaturated