School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK.
GlaxoSmithKline R&D, Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire, SG1 2NY, UK.
Angew Chem Int Ed Engl. 2019 Dec 19;58(52):18844-18848. doi: 10.1002/anie.201910276. Epub 2019 Nov 21.
Aminocyclopropanes equipped with pendant nucleophiles undergo carbonylative heterocyclization triggered by C-C bond activation to generate eight-membered N-heterocycles. In these processes, intramolecular "capture" of a rhodacyclopentanone intermediate by an aryl or N-based nucleophile is followed by C-C or C-N bond-forming "collapse" to the targets. These studies demonstrate how the combination of cyclopropane strain release and the templating effect of catalytically generated metallacycles can be harnessed to enable otherwise challenging medium ring closures.
带有取代亲核试剂的氨基环丙烷通过 C-C 键活化引发羰基杂环化反应，生成八元 N-杂环。在这些过程中，通过芳基或 N 取代亲核试剂的分子内“捕获”[Rh]-环戊酮中间体，然后进行 C-C 或 C-N 键形成的“缩合”反应得到目标产物。这些研究表明，如何结合环丙烷应变释放和催化生成的金属环的模板效应来实现具有挑战性的中环环合。
