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Enabling the Synthesis of Perfluoroalkyl Bicyclobutanes via 1,3 γ-Silyl Elimination

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Department of Chemistry, Stonehill College, 320 Washington Street, Easton, Massachusetts 02357, United States
[email protected]
‡Present address: University of Connecticut, Department of Chemistry, 55 North Eagleville Road, Unit 3060, Storrs, Connecticut 06269-3060.
§Present address: Brandeis University, Department of Biochemistry, 415 South Street, Waltham, Massachusetts 02454.
†Stonehill College.
∥Present address: Chemic Laboratories, 480 Neponset Street, Bldg. 7, Canton, Massachusetts 02021.
⊥Present address: Department of Chemistry, University of California, Berkeley, B84 Hildebrand Hall #1460, Berkeley, California 94720-1460.
#Present address: University of Wisconsin—Madison, Department of Chemistry, 1101 University Avenue, Madison, Wisconsin 53706.
Cite this: Org. Lett. 2011, 13, 7, 1646–1649
Publication Date (Web):March 2, 2011
https://doi.org/10.1021/ol200121f
Copyright © 2011 American Chemical Society
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    Abstract

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    Two new bicyclobutanes were prepared from cyclobutyl systems by a novel, solvolytic, carbocation-based methodology. An electron-withdrawing perfluoroalkyl group at the incipient cationic center enhances neighboring-group participation of the γ-silyl group, inducing facile, remarkably selective 1,3-elimination yielding only bicyclobutanes. The method unlocks potential access to a host of EWG-substituted strained rings and a potential new method for the synthesis of trifluoromethylcyclopropanes.

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    17. Petr Beier, Mikhail Zibinsky, G. K. Surya Prakash. Nucleophilic Additions of Perfluoroalkyl Groups. 2016, 1-492. https://doi.org/10.1002/0471264180.or091.01
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    20. R. A. McClelland. Carbocations. 2014, 285-301. https://doi.org/10.1002/9781118560273.ch7
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