Conjugate Addition/[3,3] Sigmatropic Shift Processes for Formation of Medium-Ring Cyclic Amines 鈥?Do They Circumvent the Woodward鈥揌offmann Rules?

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• 作者：Phillip P. Painter ; Matthew R. Siebert ; Dean J. Tantillo
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：December 4, 2015
• 年：2015
• 卷：80
• 期：23
• 页码：11699-11705
• 全文大小：503K
• ISSN：1520-6904

文摘

Herein we describe our exploration, using density functional theory calculations, of a conjugate addition鈥搑earrangement sequence that leads to medium-ring cyclic amines. On the basis of the results of our calculations, we conclude that the rearrangement step is rate determining. In addition, we analyze the role of a carbanion lone pair in the rearrangement step, concluding that it functions as a substituent on a [3,3] sigmatropic shift, rather than a nucleophile; thus, the Woodward鈥揌offmann rules are not circumvented in this reaction via involvement of orthogonal orbitals on an atom involved in the rearrangement.