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Tunable cross coupling of silanols: Selective synthesis of heavily substituted allenes and butadienes
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0002-1743-7650
2012 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 134, no 38, 15992-15999 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2012. Vol. 134, no 38, 15992-15999 p.
Keyword [en]
1, 2-dienes, 1, 3-dienes, Allenes, Allylic rearrangement, Aryl bromides, Aryl iodides, Coupling reaction, Cross-couplings, Diastereomeric, High yield, Palladium-catalyzed, Selective synthesis, Silaboration, Silanols, Site selective, Site selectivity, Substitution patterns, Suzuki-Miyaura, Butadiene, Silver oxides, Olefins, 1, 3 butadiene, alkene derivative, allene derivative, iodine derivative, silanol, article, controlled study, cross coupling reaction, diastereoisomer, quantum yield, Suzuki reaction, synthesis
National Category
Organic Chemistry
URN: urn:nbn:se:kth:diva-105327DOI: 10.1021/ja3070717ISI: 000309099700058ScopusID: 2-s2.0-84866721008OAI: diva2:570715
Swedish Research Council

QC 20121120

Available from: 2012-11-20 Created: 2012-11-20 Last updated: 2012-11-30Bibliographically approved

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