反芳香性增益使环庚三烯酮和非苯型芳烃作为正常电子需求的狄尔斯-阿尔德双烯体被激活。
Antiaromaticity Gain Activates Tropone and Nonbenzenoid Aromatics as Normal-Electron-Demand Diels-Alder Dienes.
作者信息
Karas Lucas J, Campbell Adam T, Alabugin Igor V, Wu Judy I
机构信息
Department of Chemistry, University of Houston, Houston, Texas 77204, United States.
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
出版信息
Org Lett. 2020 Sep 18;22(18):7083-7087. doi: 10.1021/acs.orglett.0c02343. Epub 2020 Aug 28.
Abstract
We propose a carbonyl umpolung strategy for activating tropone as a normal-electron-demand Diels-Alder diene. Tropone has low reactivity for Diels-Alder reactions because of its [4+2] π-aromaticity. Conversion of the carbonyl group into a hydrazone ion (═N-NR) reverses the polarity of the exocyclic double bond, increases the [4] ring π-antiaromaticity, and raises the HOMO energy. Computed gas-phase activation free energies for a Diels-Alder reaction with maleimide suggest a billion-fold rate increase when the tropone C═O is replaced by ═N-NR (R = H or SOCH). Other nonbenzenoid aromatics can be activated as normal-electron-demand Diels-Alder dienes in the same way.
摘要
我们提出了一种羰基极性反转策略，用于将环庚三烯酮作为正常电子需求的狄尔斯-阿尔德二烯进行活化。由于其[4+2]π芳香性，环庚三烯酮对狄尔斯-阿尔德反应的反应活性较低。将羰基转化为腙离子（═N-NR）可反转外环双键的极性，增加[4]环π反芳香性，并提高最高占据分子轨道（HOMO）能量。与马来酰亚胺发生狄尔斯-阿尔德反应的计算气相活化自由能表明，当环庚三烯酮的C═O被═N-NR（R = H或SOCH）取代时，反应速率提高了十亿倍。其他非苯型芳烃也可以通过同样的方式作为正常电子需求的狄尔斯-阿尔德二烯被活化。
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