手性烷氧基硅氧基烯丙基阳离子与呋喃的[4 + 3]环加成反应中立体选择性的起源。
Origin of stereoselectivity in the (4 + 3) cycloadditions of chiral alkoxy siloxyallyl cations with furan.
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
出版信息
Org Lett. 2010 Feb 5;12(3):444-7. doi: 10.1021/ol902591k.
The mechanisms and stereoselectivities of (4 + 3) cycloadditions between chiral alkoxy siloxyallyl cations and furan are examined using density functional theory calculations. These cycloadditions are predicted to take place via stepwise mechanisms. The stereoselectivities of cycloadditions involving siloxyallyl cations derived from chiral alpha-methyl benzylic alcohols are controlled by two effects: minimization of steric repulsion between the alpha-Me group and the allyl group and attractive CH-pi interactions between the furan and the aryl group.
使用密度泛函理论计算研究了手性烷氧基硅氧基烯丙基阳离子与呋喃之间的（4+3）环加成反应的机制和立体选择性。这些环加成反应被预测通过逐步机制发生。涉及手性α-甲基苄基醇衍生的硅氧基烯丙基阳离子的环加成的立体选择性受两个因素控制：α-Me 基团和烯丙基基团之间的空间排斥的最小化以及呋喃和芳基基团之间的 CH-π相互作用。
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