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Negishi's Reagent Versus Rosenthal's Reagent in the Formation of Zirconacyclopentadienes
Author(s) -
UrregoRiveros Sara,
Ramirez y Medina IsabelMaria,
Duvinage Daniel,
Lork Enno,
Sönnichsen Frank D.,
Staubitz Anne
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902255
Subject(s) - negishi coupling , reagent , moiety , chemistry , yield (engineering) , combinatorial chemistry , organic chemistry , medicinal chemistry , materials science , metallurgy
Zirconacyclopentadienes are versatile precursors for a large number of heteroles, which are accessible by Zr‐element exchange reactions. The vast majority of reports describe their preparation by the use of Negishi′s reagent, which is a species that is formed in situ. The zirconacyclopentadiene is then formed by the addition of one equivalent of a diyne or two equivalents of a monoyne moiety to this Negishi species. Another route involves Rosenthal′s reagent (Cp 2 Zr(py)Me 3 SiC≡CSiMe 3 ), which then reacts with a diyne or monoyne moiety. In this work, the efficiency of both routes was compared in terms of reaction time, stability of the product in the reaction mixture, and yield. The synthetic implications of using both routes are evaluated. Novel zirconacyclopentadienes were synthesized, characterized directly from the reaction mixture, and crystal structures could be obtained in most cases.