Tunable cross coupling of silanols

Publicerad 2012 av Hui Zhou

3 Butadiene Coupling Reaction Cross Coupling Reaction Cross-couplings Natural Sciences High Yield Olefins Silaboration Aryl Bromides Naturvetenskap Allene Derivative Quantum Yield Silanol Diastereomeric Controlled Study Suzuki-miyaura Article Substitution Patterns Palladium-catalyzed 1 Site Selective Diastereoisomer Suzuki Reaction 3-dienes Site Selectivity Iodine Derivative Silver Oxides Aryl Iodides Synthesis Selective Synthesis 2-dienes Allenes Alkene Derivative Silanols Allylic Rearrangement Butadiene
Typ av publikation: Artiklar
Typ av innehåll: Refereegranskad publ.

Ingår i:
Journal of the American Chemical Society

Published by: Kungl. Tekniska högskolan, ISSN:0002-7863,


1,3-Dienyl-2-silanols with a wide range of substitution patterns are readily obtained by palladium-catalyzed silaboration of 1,3-enynes followed by Suzuki-Miyaura cross coupling with aryl bromides. Subsequent Hiyama-Denmark cross coupling with aryl iodides provides either 1,3- or 1,2-dienes in high yields. The site selectivity can be fully controlled by the choice of activator used in the coupling reaction.

In the presence of strong bases such as NaOt-Bu, KOt-Bu, and NaH, clean formation of 1,2-dienes takes place via allylic rearrangement. In contrast, stereo- and site-selective formation of tetra- and trisubstituted 1,3-dienes results from use of Ag 2O and Bu 4NF·3H 2O, respectively, as activators. Under microwave heating at 100 °C the base-mediated cross couplings are largely accelerated and are completed within one hour or less.

The ratio of diastereomeric allenes varies depending on the substitution pattern of the silanol and ranges from >99:1 to 52:48.

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