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Kinetics and Mechanism of Pyrrolidine Buffer-Catalyzed Fulvene Formation
Paul Sieverding1, Johanna Osterbrink1, Claire Besson1,2
1Institute of Inorganic Chemistry , RWTH Aachen University , 52062 Aachen , Germany.
Abstract:
Rapid synthesis of fulvenes is achieved using pyrrolidinium/pyrrolidine buffers in anhydrous acetonitrile. Time-dependent UV-vis absorption and NMR spectroscopy reveal that the rate and yield of fulvene formation depend strongly on both the presence of acid in the medium and the choice of solvent, and they are negatively affected by water. Kinetic data have been collected for various substrates, and the synthetic benefits of the adjusted reaction conditions are showcased. Enhancements of reaction rates are found in comparison to literature procedures. α-Unsaturated fulvenes that were previously difficult to access can now be obtained in good yields.
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