Reaction of Iodonium Ylides of 1,3-Dicarbonyl Compounds with HF Reagents 英文参考文献.docVIP

Molecules 2012, 17, 6625-6632; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Reaction of Iodonium Ylides of 1,3-Dicarbonyl Compounds with HF Reagents Keisuke Gondo and Tsugio Kitamura * Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering, Saga University, Honjo-machi, Saga 840-8502, Japan * Author to whom correspondence should be addressed; E-Mail: kitamura@cc.saga-u.ac.jp; Tel.: +81-952-28-8550; Fax: +81-952-28-8548. Received: 7 May 2012; in revised form: 29 May 2012 / Accepted: 29 May 2012 / Published: 31 May 2012 Abstract: Reaction of dibenzoylmethane with (diacetoxyiodo)benzene in the presence of KOH in MeCN quantitatively gave the corresponding iodonium ylide, which was treated with a HF reagent to afford the corresponding 2-fluorinated dibenzoylmethane in 14–50% yields. The similar reaction of the iodonium ylides obtained from 1-phenylbutan-1,3-dione, ethyl benzoylacetate, and ethyl p-nitrobenzoylacetate with TEA·3HF gave the corresponding fluorinated products in 17–34% yields. It is suggested that the fluorinated products were formed through the C-protonation of the ylide, followed by displacement with fluoride ion. The same reaction of the iodonium ylide of dibenzoylmethane with concentrated HCl gave the corresponding chlorinated product in 45% yield. Keywords: iodonium ylide; hypervalent iodine; dibenzoylmethane; 1,3-dicarbonyl compound; fluorination; chlorination 1. Introduction Since an iodonium ylide was first prepared by Neilands et al. by the reaction of dimedone and (difluoroiodo)benzene [1], many iodonium ylides have been prepared, characterized, and applied to synthetic reactions [2–9]. Most of them are stabilized iodonium ylides that have two strong electron- withdrawing groups such as carbonyl, sulfonyl, cyano, and nitro groups. Unstable monocarbonyl iodonium y