通过N-连接烯丙酰胺的环氧化反应实现氮稳定的手性氧烯丙基阳离子的立体选择性分子内[4 + 3]环加成反应。
Stereoselective intramolecular [4 + 3] cycloadditions of nitrogen-stabilized chiral oxyallyl cations via epoxidation of N-tethered allenamides.
作者信息
Xiong Hui, Huang Jian, Ghosh Sunil K, Hsung Richard P
机构信息
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
出版信息
J Am Chem Soc. 2003 Oct 22;125(42):12694-5. doi: 10.1021/ja030416n.
The first intramolecular [4 + 3] cycloaddition reaction using nitrogen-stabilized chiral oxyallyl cations that are tethered to furan or diene through the nitrogen atom is described here. Formation of these nitrogen-stabilized chiral oxyallyl cations is achieved by a chemoselective epoxidation of chiral allenamides via syringe pump addition of dimethyl dioxirane. The ensuing cycloaddition can be carried out with a range of different lengths for the tether, and high diastereoselectivities can be obtained when using chiral allenamides with shorter tethers.
本文描述了首例分子内[4 + 3]环加成反应，该反应使用通过氮原子与呋喃或二烯相连的氮稳定的手性氧烯丙基阳离子。通过注射器泵添加二甲基二氧杂环丙烷对手性烯丙酰胺进行化学选择性环氧化，从而实现这些氮稳定的手性氧烯丙基阳离子的形成。随后的环加成反应可以在不同长度的连接基团下进行，并且当使用连接基团较短的手性烯丙酰胺时，可以获得高非对映选择性。
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