Preparation and Application of Solid, Salt-Stabilized Zinc Amide Enolates with Enhanced Air and Moisture Stability

Chen, Yi-Hung; Ellwart, Mario; Toupalas, Georgios; Ebe, Yusuke und Knochel, Paul (2017): Preparation and Application of Solid, Salt-Stabilized Zinc Amide Enolates with Enhanced Air and Moisture Stability. In: Angewandte Chemie-international Edition, Bd. 56, Nr. 16: S. 4612-4616

Abstract

The treatment of various N-morpholino amides with TMPZnCl center dot LiCl (TMP= 2,2,6,6-tetramethylpiperidyl) and Mg(OPiv)(2) in THF at 25 degrees C provides solid zinc enolates with enhanced air and moisture stability (t(1/2) in air: 1-3 h) after solvent evaporation. These enolates undergo Pd-and Cucatalyzed cross-couplings with (hetero) aryl bromides as well as allylic and benzylic halides. The arylated N-morpholino amides were converted into various ketones by LaCl3 center dot 2 LiCl mediated acylation with Grignard reagents. The new, solid enolates were used to prepare a potent anti-breast-cancer drug candidate in six steps and 23% overall yield.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1433-7851
• Sprache: Englisch