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DOI: 10.1055/sos-SD-219-00200

Kirschning, A.; Gille, F.; Wolling, M.Science of Synthesis: Applications of Domino Transformations in Organic Synthesis, (20151444.

The Brook rearrangement can be categorized as classic and the transformation itself seems to be rather simple. Originally it was thought to have little impact on organic synthesis. Probably as a consequence, only few mechanistic studies have been reported over the decades.[‌154‌,‌155‌] These mainly cover the retro-1,2-Brook rearrangement. Since the early 1990s, the Cinderella status of the Brook rearrangement has changed because the Brook rearrangement has been embedded into domino reaction sequences. The value of this reaction is connected with the fact that an easily available oxyanion is transformed into a valuable carbanionic species which can further be exploited in carbon–carbon coupling reactions. Now, the large variety of different examples and applications available, including complex natural product syntheses, are due to a deeper understanding of how to efficiently initiate silyl migration (the well-balanced stabilization of the newly formed carbanionic species is crucial here) and the large number of methods to create an alkoxide anion. This has changed the relevance of the Brook rearrangement drastically. Indeed, one can expect many sophisticated applications in the future.