通过极性和自由基机制实现2-氮杂烯丙基与烯丙基醚的无过渡金属烯丙基化反应。
Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms.
作者信息
Deng Guogang, Duan Shengzu, Wang Jing, Chen Zhuo, Liu Tongqi, Chen Wen, Zhang Hongbin, Yang Xiaodong, Walsh Patrick J
机构信息
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; Yunnan Provincial Center for Research & Development of Natural Products, School of Chemical Science and Technology, Yunnan University, Kunming, P. R. China.
Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA.
出版信息
Nat Commun. 2021 Jun 23;12(1):3860. doi: 10.1038/s41467-021-24027-6.
Allylation of nucleophiles with highly reactive electrophiles like allyl halides can be conducted without metal catalysts. Less reactive electrophiles, such as allyl esters and carbonates, usually require a transition metal catalyst to facilitate the allylation. Herein, we report a unique transition-metal-free allylation strategy with allyl ether electrophiles. Reaction of a host of allyl ethers with 2-azaallyl anions delivers valuable homoallylic amine derivatives (up to 92%), which are significant in the pharmaceutical industry. Interestingly, no deprotonative isomerization or cyclization of the products were observed. The potential synthetic utility and ease of operation is demonstrated by a gram scale telescoped preparation of a homoallylic amine. In addition, mechanistic studies provide insight into these C(sp)-C(sp) bond-forming reactions.
亲核试剂与烯丙基卤化物等高活性亲电试剂的烯丙基化反应可以在无金属催化剂的情况下进行。活性较低的亲电试剂，如烯丙基酯和碳酸酯，通常需要过渡金属催化剂来促进烯丙基化反应。在此，我们报道了一种独特的无过渡金属的烯丙基化策略，该策略使用烯丙基醚亲电试剂。一系列烯丙基醚与2-氮杂烯丙基阴离子反应生成了有价值的高烯丙基胺衍生物（产率高达92%），这些衍生物在制药行业具有重要意义。有趣的是，未观察到产物的去质子异构化或环化现象。通过克级串联制备高烯丙基胺证明了该方法潜在的合成实用性和操作简便性。此外，机理研究为这些C(sp)-C(sp)键形成反应提供了深入见解。
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