Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume 2009, Issue 19, Pages 3219-3227Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.200900288
Keywords
Acylation; Cross-coupling; Rhodium; Palladium; Ketones
Categories
Funding
- French Ministere de l'Education Nationale de la Recherche et de la Technologie (MENRT)
- Polymer Laboratories, Ltd. and the European Commision [MCRTN-CT-2003-5050201]
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The synthesis and application of (E)-1,2-disilylethene 5 as a central functional building block in a sequential Hiyama coupling/Narasaka acylation reaction are described. Its use in the rapid and versatile construction of a,p-unsaturated carbonyl motifs found in a number of polyunsaturated natural products has been demonstrated. It was observed that due to the differential intrinsic reactivity of the two carbon-silicon bonds, this bis-metallated lynchpin-type reagent is activated selectively and sequentially by Pd and Rh catalysis, negating the need for any protecting group. A number of (E)-alpha,beta-unsaturated ketones were efficiently synthesized with complete chemoselectively in the presence of a variety of halides and anhydride acids. Conjugated polyunsaturated ketones and diversely alpha'-functionalized alpha,beta-enones, such as chalcones, a heterocyclic dienone and the highly conjugated ethyl (2Z,4E)-6-oxo-6-(2-thienyl)hexa-2,4-dienoate, were obtained in good overall yields. Thus, this coupling sequence provides a high degree of modularity, that is, a single template is likely to produce a large number of synthetic targets. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
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