The origin of endo stereoselectivity in the hetero-diesl-alder reactions of aldehydes with ortho-xylylenes: CH-pi, pi-pi, and steric effects on stereoselectivity

Gregori Ujaque; Patrick S.Lee; K.N.Houk; Martin F.Hentemann; Samuel J.Danishefsky

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The origin of endo stereoselectivity in the hetero-diesl-alder reactions of aldehydes with ortho-xylylenes: CH-pi, pi-pi, and steric effects on stereoselectivity

机译：醛与邻二甲苯的异二烯醛反应中的内立体选择性的起源：CH-pi，pi-pi和立体选择性的空间效应

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Theoretical stueies of stereoselectivity have been carried out with B3LYP and MP2 calculations. The high endo selectivity of hetero-Diels-Alder reactions of ortho-xylylenes with acetaldehydes is shown to result from attractive CH-pi interactions between alkyl groups of the aldehyde and the aromatic ring in the transition states of the reaction. For the hetero-Diels-Alder reactions of ortho-xylylenes with benzaldehyde, the stereoselectivity is shown to be mainly governed by the attractive pi-pi interactions between the phenyl rings of the benzaldehyde and the ortho-xylylene. MP2 calculations are necessary to reproduce the stabilizing dispersion interactions.

机译：立体选择性的理论研究已经通过B3LYP和MP2计算进行了。已表明，邻二甲苯与乙醛的杂Diels-Alder反应具有较高的内选择性，这是由于在反应的过渡态下，醛的烷基与芳环之间有吸引力的CH-pi相互作用所致。对于邻二甲苯与苯甲醛的杂Diels-Alder反应，立体选择性主要受苯甲醛与邻二甲苯苯环之间有吸引力的pi-pi相互作用支配。 MP2计算对于重现稳定的色散相互作用是必需的。

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《Chemistry: A European journal》 |2002年第15期|共8页
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Gregori Ujaque; Patrick S.Lee; K.N.Houk; Martin F.Hentemann; Samuel J.Danishefsky;
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正文语种 eng
中图分类化学;应用化学;
关键词
ab initio calculations; cycloaddition; pi interactions; stacking interactions; stereoselectivity;

机译：从头算;环加成;π相互作用;堆积相互作用;立体选择性;

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1. The origin of endo stereoselectivity in the hetero-diesl-alder reactions of aldehydes with ortho-xylylenes: CH-pi, pi-pi, and steric effects on stereoselectivity [J] . Gregori Ujaque, Patrick S.Lee, K.N.Houk, Chemistry: A European journal . 2002,第15期

机译：醛与邻二甲苯的异二烯醛反应中的内立体选择性的起源：CH-pi，pi-pi和立体选择性的空间效应
2. Origin of the Endo/Exo Stereoselectivity and Syn/Anti Face-Selectivity in Diels-Alder Reactions,Determined by Transition State Energy Partitioning [J] . Shingo Kiri, Huda Izzat Omar, Tetsuro Shimo, Bulletin of the Chemical Society of Japan . 2004,第8期

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The origin of endo stereoselectivity in the hetero-diesl-alder reactions of aldehydes with ortho-xylylenes: CH-pi, pi-pi, and steric effects on stereoselectivity

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