ol8b03875_si_001.pdf (4.32 MB)
One-Step Synthesis of Diaza Macrocycles by Rh(II)-Catalyzed [3 + 6 + 3 + 6] Condensations of Morpholines and α‑Diazo-β-ketoesters
journal contribution
posted on 2019-01-18, 20:13 authored by Alexandre Homberg, Daniele Poggiali, Mahesh Vishe, Céline Besnard, Laure Guénée, Jérôme LacourSelective formation
of oxonium ylides from morpholines and α-diazo-β-ketoesters
was achieved. This was applied to the high-concentration (0.5 M) dirhodium-catalyzed
(0.1 mol %) [3 + 6 + 3 + 6] synthesis of 18-membered ring diaza
macrocycles (46%–72%). Late-stage functionalization of these
derivatives is demonstrated. Mechanistic evidence for a novel (undesired)
diazo decomposition pathway is also reported.