镍催化芳基2-氮杂烯丙基阴离子的对映选择性乙烯基化反应。
Nickel-catalyzed enantioselective vinylation of aryl 2-azaallyl anions.
作者信息
Duan Shengzu, Deng Guogang, Zi Yujin, Wu Xiaomei, Tian Xun, Liu Zhengfen, Li Minyan, 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 650091 P. R. China
Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania 231 South 34th Street Philadelphia PA USA
出版信息
Chem Sci. 2021 Mar 26;12(18):6406-6412. doi: 10.1039/d1sc00972a.
A unique enantioselective nickel-catalyzed vinylation of 2-azaallyl anions is advanced for the first time. This method affords diverse vinyl aryl methyl amines with high enantioselectivities, which are frequently occurring scaffolds in natural products and medications. This C-H functionalization method can also be extended to the synthesis of enantioenriched 1,3-diamine derivatives by employing suitably elaborated vinyl bromides. Key to the success of this process is the identification of a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, all of which favor an anionic vinylation route over a background radical reaction. A telescoped gram scale synthesis and a product derivatization study confirmed the scalability and synthetic potential of this method.
首次提出了一种独特的镍催化对映选择性2-氮杂烯丙基阴离子乙烯基化反应。该方法能以高对映选择性得到多种乙烯基芳基甲胺，这些结构在天然产物和药物中经常出现。通过使用适当修饰的乙烯基溴化物，这种C-H官能团化方法还可扩展到对映体富集的1,3-二胺衍生物的合成。该反应成功的关键在于确定了一种镍/手性膦催化剂体系以及一种还原性较弱的2-氮杂烯丙基阴离子，所有这些都有利于通过阴离子乙烯基化途径而非背景自由基反应。克级规模的连续合成和产物衍生化研究证实了该方法的可扩展性和合成潜力。
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