Proceedings of the Japan Academy, Series B
Online ISSN : 1349-2896
Print ISSN : 0386-2208
ISSN-L : 0386-2208
Reviews
Development of β-keto ester and malonate chemistry
Palladium-catalyzed new reactions of their allylic esters
Jiro TSUJI
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ジャーナル フリー

2004 年 80 巻 8 号 p. 349-358

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During extensive studies on π-allylpalladium chemistry, we have developed classical β-keto ester and malonate chemistry to a new generation by discovering a variety of palladium-catalyzed reactions of their allylic esters. Palladium enolates are generated from allyl β-keto esters after decarboxylation and undergo the following transformations; a) reductive elimination to provide α-allyl ketones, b) elimination of β-hydrogen to give α, β-unsaturated ketones, c) formation of α-methylene ketones, d) hydrogenolysis to give ketones, e) aldol condensation, and f) Michael addition. Allyl malonates and cyanoacetes undergo similar reactions. Results of these studies, including several applications carried out by other researchers are summarized.


(Communicated by Teruaki MUKAIYAMA, M.J.A.)
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© 2004 The Japan Academy
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