期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 130, 期 50, 页码 17161-17167出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja805657h
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资金
- MEXT (KAKENHI) [18105004]
- Global COE Program for Chemistry Innovation
- Japan Society for the Promotion of Science (JSPS) for a Research Fellowship for Young Scientists [18-9971]
Lewis acidic indium(III) salts, in particular In(NTf2)(3), effect the conversion of alpha-(omega'-alkynyl)-beta-ketoesters; and omega-alkynyl-beta-ketoesters to the corresponding cyclic products in a manner known as the Coniaene reaction. This reaction can lead to the creation of five- to fifteen-membered-ring carbocycles and heterocycles in good to excellent yields. The synthetic features of the reaction are a relatively low catalyst loading, as low as 0.01 mol % in the best case, as well as no requirement of solvent for five-membered-ring formation and the requirement of only moderately dilute reaction conditions for medium-sized-ring formation. The high reactivity of indium salts is due to the double activation of the beta-ketoester substrate containing an acetylene function. The indium metal activates the beta-ketoester moiety by the formation of an indium enolate, and this indium metal electrophilically activates the alkyne moiety. Such a strong push-pull activation of the substrate by a single metal circumvents the disadvantage of entropic and enthalpic factors generally associated with the formation of medium- and large-sized rings. The reaction allows the ready formation of a fifteen-membered-ring carbocycle, from which di-muscone has been synthesized.
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