Efficient Access to Titanaaziridines by C-H Activation of N-Methylanilines at Ambient Temperature
Efficient Access to Titanaaziridines by C-H Activation of N-Methylanilines at Ambient Temperature
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DOI：
10.1002/anie.201500796
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发表时间：
2015-03-27
影响因子：
16.6
通讯作者：
Beckhaus, Ruediger
中科院分区：
文献类型：
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作者：
Manssen, Manfred;Lauterbach, Nicolai;Beckhaus, Ruediger
钛氮杂环丙烷或η（2）-亚胺钛配合物被认为是钛催化烯烃氢氨烷基化的关键中间体。在此，我们提出了一种有效的合成路线，这类化合物，从N-甲基苯胺和双（eta（5）：eta（1）-pentafulvene）钛配合物。首次表征了eta（2）-亚甲基苯胺配合物上的连续反应，证明了其高度的化学通用性。特别地，在三元钛环与烯烃的反应中发现了加氢氨基烷基化产物。首次对烯烃氢氨烷基化反应的所有中间体进行了分离和表征。
Titanaaziridines or eta(2)-imine titanium complexes are considered key intermediates of the titanium-catalyzed hydroaminoalkylation of alkenes. Herein, we present an efficient synthetic route to this class of compounds, starting from N-methylanilines and a bis(eta(5):eta(1)-pentafulvene) titanium complex. Consecutive reactions on the eta(2)-methyleneaniline complexes, characterized for the first time, prove a high chemical versatility. In particular, hydroaminoalkylation products were found in reactions of the three-membered titanacycles with alkenes. For the first time, all the intermediates of the hydroaminoalkylation of alkenes were isolated and characterized.