Journal
TETRAHEDRON
Volume 71, Issue 37, Pages 6594-6601Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.tet.2015.07.002
Keywords
Palladium; Enolate; beta-Ketoamide; Michael reaction; Fluorination
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Funding
- RIKEN
- Japan Science and Technology Agency
- Japan Society for the Promotion of Science KAKENHI grant [26560439]
- AMED-CREST, AMED
- Junior Research Associate (JRA) program in RIKEN
- Grants-in-Aid for Scientific Research [26560439] Funding Source: KAKEN
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We have previously reported enantioselective reactions of 1,3 -diketones and beta-ketoesters with various electrophiles catalyzed by chiral Pd complex, in which chiral Pd enolates play a key role. Here, we present a detailed examination of Pd-catalyzed enantioselective Michael addition and fluorination reactions of beta-ketoamides. beta-Ketoamide showed higher reactivity than 1,3-diketone and beta-ketoester, though its alpha-proton is likely to be least acidic. Pd enolate formation of beta-ketoamide was much faster than that of beta-ketoester. The crystal structures of (R)-BINAP-Pd-diketone and ketoamide complexes were found to be quite distinct. Pd-diketone complex has bidentate square-planar geometry as have been predicted before, whereas Pd-ketoamide complex was greatly distorted, probably due to steric constraints of the amide bond. (C) 2015 Elsevier Ltd. All rights reserved.
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