Synthesis and chemical reactivity of methoxycarbonyl-1,3-dioxinyl(pivaloyl)ketene—a persistent α-oxoketene
Synthesis and chemical reactivity of methoxycarbonyl-1,3-dioxinyl(pivaloyl)ketene—a persistent α-oxoketene
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DOI：
10.1039/b111143d
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发表时间：
2002-02
期刊：
影响因子：
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通讯作者：
Bianca C. Wallfisch;F. Belaj;C. Wentrup;C. Kappe;G. Kollenz
中科院分区：
文献类型：
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作者：
Bianca C. Wallfisch;F. Belaj;C. Wentrup;C. Kappe;G. Kollenz
4-甲氧基呋喃-5-叔丁基呋喃-2，3-二酮等摩尔混合物的闪速真空热解得到了新的非常稳定的α-甲氧基酮6，这是由于最初形成的单体α-甲氧基酮1和3发生了不寻常的二聚反应而得到的。[2+2]6和二烷基碳二亚胺的环加成反应提供了功能化的亚氨基-β-内酰胺7，而与亲核试剂的反应导致6完全降解成更小的碎片。化合物6和7的结构确认主要基于单晶X射线分析。
Flash vacuum pyrolysis of an equimolar mixture of 4-pivaloyl- and 4-methoxycarbonyl-5-tert-butylfuran-2,3-dione affords the new and remarkably stable α-oxoketene 6 as the result of an unusual dimerization of the primarily formed monomeric α-oxoketenes 1 and 3, respectively. [2 + 2] Cycloaddition reactions of 6 and dialkylcarbodiimides furnish functionalized imino-β-lactams 7, while reaction with nucleophiles results in complete degradation of 6 into smaller fragments. Structural confirmation of 6 and 7 is mainly based upon single crystal X-ray analyses.