Metal-mediated dearomatization leading to 2-azaspiro[4.5]decanes via tandem nucleophilic aromatic addition–Horner–Wadsworth–Emmons olefination–oxidative demetalation sequences |
| |
Authors: | F. Christopher Pigge Rashmi Dalvi |
| |
Affiliation: | aDepartment of Chemistry, University of Iowa, Iowa City, IA 52242, United States |
| |
Abstract: | A ruthenium-mediated dearomatization sequence has been developed that delivers structurally intriguing azaspirolactam products in stereoselective fashion. Treatment of (η6-arene)Ru(cyclopentadienyl) complexes bearing N-benzyl-β-amido phosphonate side chains with excess NaH results in intramolecular nucleophilic aromatic addition to the ipso position of the coordinated arenes. Subsequent Horner–Wadsworth–Emmons (HWE) reaction with added aldehydes affords olefinated spirolactam cyclohexadienyl ruthenium complexes. Mild oxidation with CuCl2 or CuBr2 under CO effects removal and recovery of the CpRu(II) fragment. Substituents present on the cyclohexadienyl skeleton influence the outcome of demetalation and products obtained in this study include functionalized 2-azaspiro[4.5]decanes and tetrahydroisoquinolinones. |
| |
Keywords: | Dearomatization Arene ruthenium Horner– Wadsworth– Emmons reaction Spirocyclization Oxidative demetalation |
本文献已被 ScienceDirect 等数据库收录! |