立体效应与芳炔扭曲竞争控制亲核加成到 3-硅基芳炔的区域选择性。
Steric effects compete with aryne distortion to control regioselectivities of nucleophilic additions to 3-silylarynes.
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
出版信息
J Am Chem Soc. 2012 Aug 29;134(34):13966-9. doi: 10.1021/ja306723r. Epub 2012 Aug 15.
Abstract
We report an experimental and computational study of 3-silylarynes. The addition of nucleophiles yield ortho-substituted products as a result of aryne distortion, but meta-substituted products form predominately when the nucleophile is large. Computations correctly predict the preferred site of attack observed in both nucleophilic addition and cycloaddition experiments. Nucleophilic additions to 3-tert-butylbenzyne, which is not significantly distorted, give meta-substituted products.
摘要
我们报告了 3-硅基芳炔的实验和计算研究。亲核试剂的加成产生邻位取代产物，这是芳炔变形的结果，但当亲核试剂较大时，主要形成间位取代产物。计算正确预测了亲核加成和环加成实验中观察到的优先攻击位点。对 3-叔丁基苯炔（其未显著变形）的亲核加成得到间位取代产物。
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3
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