Titanocene difluorides can be obtained by halide metathesis of the respective titanocene dichlorides with trimethyltin fluoride (Me(3)SnF), giving access to a new class of cytotoxic active substances. Furthermore, an improved method for the synthesis of diaryl-substituted titanocene dichlorides is presented.
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http://dx.doi.org/10.1021/ic9022163 | DOI Listing |
Chem Asian J
November 2016
Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstrasse 34-36, 14195, Berlin, Germany.
Several functionalized and non-functionalized perfluoroarenes were catalytically transformed into their para-hydrodefluorinated products by using catalytic amounts of titanocene difluoride and stoichiometric amounts diphenylsilane. Turnover numbers of up to 93 were observed. Solution density functional theory calculations at the M06-2X/TZ(PCM)//M06-2X/TZ(PCM) level of theory provided insight into the mechanism of Ti -catalyzed aromatic hydrodefluorination.
View Article and Find Full Text PDFInvest New Drugs
October 2015
Regional Centre for Applied and Molecular Oncology, Masaryk Memorial Cancer Institute, Zluty kopec 7, 65653, Brno, Czech Republic.
Background: Ovarian cancer is the seventh-most common cancer amongst women and the most deadly gynecologic cancer. Cisplatin based drugs are used in first line therapy, but resistance represents a major obstacle for successful treatment. In this study, we investigated the anticancer effects and mechanism of action of three titanocene difluorides, two bearing a pendant carbohydrate moiety (α-D-ribofuranos-5-yl) on their periphery and one without any substitution.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2010
Freie Universität Berlin, Institut für Chemie und Biochemie, Anorganische Chemie, Berlin, Germany.
Detox: air-stable titanocene difluoride efficiently catalyzes the chemoselective hydrodefluorination of fluoroalkenes at room temperature leading to hydrofluoroalkenes in high yields (see scheme: Cp=cyclopentadienyl). This is a rare example of the catalyzed conversion of fluoroalkenes into less-fluorinated compounds, which have a lower climatic impact, and is a potential method for breaking down toxic perfluoroalkenes.
View Article and Find Full Text PDFInorg Chem
February 2010
Fachbereich Chemie and Konstanz Research School Chemical Biology, Universität Konstanz, Germany.
Titanocene difluorides can be obtained by halide metathesis of the respective titanocene dichlorides with trimethyltin fluoride (Me(3)SnF), giving access to a new class of cytotoxic active substances. Furthermore, an improved method for the synthesis of diaryl-substituted titanocene dichlorides is presented.
View Article and Find Full Text PDFJ Org Chem
November 1997
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139.
A convenient method for the conversion of lactones to lactols is described. The hydrosilylation to lactols is carried out via air-stable titanocene difluoride or a titanocene diphenoxide precatalyst using inexpensive polymethylhydrosiloxane (PMHS) as the stoichiometric reductant. These procedures have been demonstrated with a variety of substrates and proceed in good to excellent yield.
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