Hydroamination of 1,1-dimethylallene with primary aryl amines under mild conditions: An atom-economical route to N-(1,1-dimethyl-2-propenyl)-anilines
Hydroamination of 1,1-dimethylallene with primary aryl amines under mild conditions: An atom-economical route to N-(1,1-dimethyl-2-propenyl)-anilines
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DOI：
10.1039/c1ra00795e
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发表时间：
2012-01-01
期刊：
影响因子：
3.9
通讯作者：
Schmidt, Joseph A. R.
中科院分区：
文献类型：
--
作者：
Beck, John F.;Schmidt, Joseph A. R.
脂环族 3-亚氨基膦配体的合成得到了扩展，包括一个新的框架，该框架结合了具有二叔丁基膦官能团的环戊烯基主链 (3IP(tBu))。钯配合物[(3IP(tBu))Pd(烯丙基)]OTf在3-甲基-1,2-丁二烯(1,1-二甲基丙二烯)与伯芳基胺(苯胺)的100%原子效率氢胺化中表现出优异的催化活性，在环境温度下以高转化率选择性地为非卤化底物生成支化烯丙胺产物(动力学产物)。使用卤代苯胺的加氢胺化在 70 摄氏度下成功，提供了中等产率，几乎没有或没有形成线性产物（热力学产物）。此外，随后使用催化三氟甲磺酸对选定的烯丙胺产物进行芳香氨基克莱森重排，被证明是一种有效的原子经济方法，用于在高产率的两步一锅合成中生产邻位烯丙苯胺。
The synthesis of alicyclic 3-iminophosphine ligands was extended to include a new framework incorporating a cyclopentenyl backbone with a di-tert-butyl phosphine functionality (3IP(tBu)). The palladium complex [(3IP(tBu))Pd(allyl)]OTf displayed excellent catalytic activity in the 100% atom-efficient hydroamination of 3-methyl-1,2-butadiene (1,1-dimethylallene) with primary aryl amines (anilines), selectively producing the branched allylic amine products (kinetic products) in high conversion at ambient temperature for non-halogenated substrates. Hydroamination using halogenated anilines was successful at 70 degrees C, providing moderate yields, with the formation of little or no linear product (thermodynamic product). Additionally, a subsequent aromatic amino Claisen rearrangement of selected allylic amine products, employing catalytic triflic acid, proved to be an effective atom-economical method for the production of ortho-allylic anilines in a high yielding two-step, one-pot synthesis.