Nonconcerted Cycloaddition of 2H-Azirines to Acylketenes: A Route to N-Bridgehead Heterocycles

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• 作者：Alexander F. Khlebnikov ; Mikhail S. Novikov ; Viktoriia V. Pakalnis ; Dmitry S. Yufit
• 刊名：Journal of Organic Chemistry
• 出版年：2011
• 出版时间：November 18, 2011
• 年：2011
• 卷：76
• 期：22
• 页码：9344-9352
• 全文大小：464K
• 年卷期：v.76,no.22(November 18, 2011)
• ISSN：1520-6904

文摘

Reactions of acylketenes, generated from diazo diketones, with 2-unsubstituted and 2-monosubstituted 3-aryl-2H-azirines lead to 1:1 or 2:1 adducts, which are derivatives of 5-oxa-1-azabicyclo[4.1.0]hept-3-ene or 5,7-dioxa-1-azabicyclo[4.4.1]undeca-3,8-diene. According to DFT B3LYP/6-31G(d) computations, the formation of (4+2)-monoadducts proceeds via a stepwise non-pericyclic mechanism. Reaction with methanol transforms quantitatively both 1:1 and 2:1 adducts into 1,4-oxazepine derivatives.