Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium.
Org Biomol Chem. 2021 May 12;19(18):4067-4075. doi: 10.1039/d1ob00404b.
An efficient metal-free strategy for the synthesis of α-substituted homoallylamine derivatives has been developed via a 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-promoted 2-aza-Cope rearrangement of aldimines, generated in situ by condensation of aldehydes with easily accessible 1,1-diphenylhomoallylamines. This reaction provides rapid access to α-substituted homoallylamines with excellent functional group tolerance and yields. The reaction takes place at room temperature and no chromatographic purification is required for product isolation. The synthetic utility of the current method is further demonstrated by the transformation of the obtained benzophenone ketimines into N-unprotected homoallylamines, an α-amino alcohol and an α-amino amide.
已开发出一种通过醛与易得的 1,1-二苯基同丙烯胺缩合原位生成的亚胺的 1,1,1,3,3,3-六氟-2-丙醇 (HFIP) 促进的 2-氮杂-Cope 重排来合成 α-取代的同丙烯胺衍生物的高效无金属策略。该反应可快速获得具有出色官能团耐受性和产率的 α-取代的同丙烯胺。反应在室温下进行，产物分离不需要色谱纯化。当前方法的合成实用性通过将获得的二苯甲酮亚胺转化为 N-未保护的同丙烯胺、α-氨基醇和α-氨基酰胺得到进一步证明。
