Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes
Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes
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DOI：
10.1021/acscatal.8b01914
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发表时间：
2018-08
期刊：
影响因子：
12.9
通讯作者：
Sangjune Park;Steven J. Malcolmson
中科院分区：
文献类型：
--
作者：
Sangjune Park;Steven J. Malcolmson
我们报道了具有高度对映性和区域选择性的pd催化的挑战性1,4-二取代无环二烯的分子间氢胺化反应的发展。几种芳基/烷基二取代二烯和一种立体分化的烷基/烷基二取代二烯与多种仲脂肪胺、吲哚和伯胺偶联，生成具有无数α-烷基的烯丙胺，产率高达78%，bbb98:2 rr和98.5:1.5 er。许多实验，包括氘标记和转氨研究，揭示了反应的机理细节，例如所提出的催化循环的各个步骤和整个反应的可逆性。
We report the development of highly enantio- and regioselective Pd-catalyzed intermolecular hydroaminations of challenging 1,4-disubstituted acyclic dienes. Several aryl/alkyl-disubstituted dienes and a sterically differentiated alkyl/alkyl-disubstituted diene undergo coupling with a variety of secondary aliphatic amines, indoline, and primary anilines to generate allylic amines with myriad α-alkyl groups in up to 78% yield, >98:2 rr, and 98.5:1.5 er. A number of experiments, including deuterium labeling and transamination studies, shed light on mechanistic details of the reaction, such as the reversibility of individual steps of the proposed catalytic cycle and of the reaction as a whole.