New Zirconocene-Coupling Route to Large, Functionalized Macrocycles

The development of a new macrocyclization reagent, Rosenthal's Cp2Zr(pyr)(Me3SiC⋮CSiMe3), has allowed the preparation of two large, functionalized macrocycles. The diyne 5,5‘-bis(4-trimethylsilylphenyl)-2,2‘-bipyridine was trimerized to the bipyridine-containing macrocycle 5, and 1,4-bis(4-(tri...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Journal of the American Chemical Society 2000-10, Vol.122 (42), p.10345-10352
Hauptverfasser: Nitschke, Jonathan R, Zürcher, Stefan, Tilley, T. Don
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:The development of a new macrocyclization reagent, Rosenthal's Cp2Zr(pyr)(Me3SiC⋮CSiMe3), has allowed the preparation of two large, functionalized macrocycles. The diyne 5,5‘-bis(4-trimethylsilylphenyl)-2,2‘-bipyridine was trimerized to the bipyridine-containing macrocycle 5, and 1,4-bis(4-(trimethylsilyl)ethynyl-phenyl)-2,3-diphenyl-1,4-diazabuta-1,3-diene was dimerized to macrocycle 6. Both zirconocene-containing macrocycles were characterized by single-crystal X-ray diffraction. Macrocycle 5, which is cleanly converted to air-stable cyclophane 7 with benzoic acid, has a cavity of van der Waals radius 6.03 Å. In general, the Cp2Zr(pyr)(Me3SiC⋮CSiMe3) reagent gives higher yields of macrocycles via the coupling of diynes than does the reagent generated by addition of n-BuLi to Cp2ZrCl2.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0020310