The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable, Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU, UK.
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Chemistry. 2018 Sep 12;24(51):13432-13436. doi: 10.1002/chem.201803574. Epub 2018 Aug 20.
Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give Z-homoallylic alcohols and amines, respectively.
金属通过碳链迁移是实现远程功能化的一种通用方法。然而，几乎所有已知的例子都涉及烷基金属物种的整体净迁移。在这里，我们报告说，从 1,3-二烯的水合氢化得到的烯丙基铑物种向酯、酰胺或（杂）芳烃进行链迁移，距离长达 8 个亚甲基单元。最终，更高度共轭的烯丙基铑物种与醛和亚胺进行亲核烯丙基化，分别得到 Z-高烯丙醇和胺。
