Hydrocarbation of C C Bonds: Quantification of the Nucleophilic Reactivity of Ynamides**
Hydrocarbation of C C Bonds: Quantification of the Nucleophilic Reactivity of Ynamides**
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DOI：
10.1002/anie.201402055
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发表时间：
2014-05-05
影响因子：
16.6
通讯作者：
Mayr, Herbert
中科院分区：
文献类型：
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作者：
Laub, Hans A.;Evano, Gwilherm;Mayr, Herbert
给电子体取代的二芳基卡宾离子Ar2CH+与氰胺反应生成1-氨基取代的烯丙基阳离子(，-不饱和亚胺离子)。动力学研究表明，这些加合物对应于在CC键上加成一个CH键，是随着酮亚胺离子的初始形成和随后的1，3-氢化物移动而逐步形成的。二阶速率常数(lgk(2)，20℃)与二芳基卡宾离子的亲电性参数E之间的线性关联使我们能够在我们的综合亲核性标度中包括亚硝胺，从而预测潜在的亲电反应伙伴。
Donor-substituted diarylcarbenium ions Ar2CH+ react with ynamides to give 1-amido-substituted allyl cations (,-unsaturated iminium ions). Kinetic studies show that these adducts, which correspond to the addition of a CH bond across the CC bond, are formed stepwise with initial formation of keteniminium ions and subsequent 1,3-hydride shifts. The linear correlations between the second-order rate constants (lgk(2), 20 degrees C) with the electrophilicity parameters E of the diarylcarbenium ions allow us to include ynamides in our comprehensive nucleophilicity scale and thus predict potential electrophilic reaction partners.