Hyperconjugative, Secondary Orbital, Electrostatic, and Steric Effects on the Reactivities and Endo and Exo Stereoselectivities of Cyclopropene Diels-Alder Reactions

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作者：
Levandowski, Brian J. [1 ]
Houk, K.N. [1 ]
机构：
[1] Department of Chemistry and Biochemistry, University of California, Los Angeles,California,90095, United States
来源：
Journal of the American Chemical Society | 2016年 / 138卷 / 51期
关键词：
The factors controlling the reactivities and stereoselectivities in the Diels-Alder reactions of substituted cyclopropenes with butadiene were explored with M06-2X density functional theory. Differences in reactivities result from differences in the hyperconjugative aromaticities and antiaromaticities of the cyclopropenes. When the 3-substituent is a σ-donor; the ground state is destabilized; and the reactivity is enhanced. Acceptors have the opposite effect. Electrostatic; secondary orbital; and steric effects are all found to influence stereoselectivities. © 2016 American Chemical Society;
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页码：16731 / 16736
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