Beyond Corey Reagents: A New Route to Key Intermediates and Materials
Final Report Abstract
For a long time it was generally believed that sulfur ylides and dimsyl reagents are not very stable, and heating above 80 °C causes their fast decomposition. As a result, most sulfur ylide transformations were studied in the temperature interval from 0 to 80 °C, as in the classic Corey reaction. This situation changed after the direct diolefination of ketones in the dimsyl sodium/dimethylsulfoxonium methylide system at 130 °C was discovered. Besides the diolefination reaction, we have found several other high-temperature transformations involving sulfur ylides that are not only fundamentally important, but also useful for preparative organic chemistry. Within this project we found two new reactions, namely ring expansions in oxetanes to oxolanes, and direct dimethylenation of methyl ketones that occur only at 130 °C. Several other groups are now exploring the high-temperature chemistry of dimsyl sodium. For instance, the reaction of dimsyl sodium for dehydrobromination 3-oxygenated 4-bromopiperidines at temperatures as high as 150 °C was explored and it turns out that high-temperature ylide chemistry has not yet been fully explored.
Publications
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Beyond the Corey reaction: One-Step diolefination of cyclic ketones. J. Org. Chem. 2007, 72, 5689–5696
Butova, E. D.; Fokin, A. A.; Schreiner, P. R.
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Simple preparation of diamondoid 1,3-dienes via oxetane ring opening. Org. Lett. 2007, 9, 2541–2544.0
Fokin, A. A.; Butova, E. D.; Chernish, L. V.; Fokina, N. A.; Dahl, J. E. P.; Carlson, R. M. K.; Schreiner, P. R.
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Stereospecific consecutive epoxide ring expansion with dimethylsulfoxonium methylide. J. Org. Chem. 2010, 75, 18, 6229–6235
Butova, E. D.; Barabash, A. V.; Petrova, A. A.; Kleiner, C. M.; Schreiner, P. R.; Fokin, A. A.
