N-Allylhydrazones are an extremely useful, but under-explored synthetic intermediate. These compounds undergo [3,3] sigmatropic rearrangements, forging a new carbon–carbon bond and extruding nitrogen gas. The oxidative potential of these compounds has been explored and shown to lead to novel transformations where the initial functionality of the starting materials has vanished, resulting in traceless bond construction.
N-Bromosuccinimide has shown to be a useful oxidant in effecting the [3,3] sigmatropic rearrangement of N-allylhydrazones, affording tandem carbon–carbon and carbon–bromine bond formation. The forming bromide can be eliminated in situ resulting in a one-pot, highly stereoselective diene synthesis.
Hypervalent iodide compounds have also shown to be effective oxidants of N-allylhydrazones, resulting in our development of a modular three component fragment coupling cascade reaction. This method has been applied to the total syntheses of aryltetralone lignans isolated from Holostylis reniformis. A variety of these natural products are readily accessed from a common intermediate.
|Advisor:||Thomson, Regan J.|
|Commitee:||Scheidt, Karl, Silverman, Richard|
|School Location:||United States -- Illinois|
|Source:||DAI-B 74/05(E), Dissertation Abstracts International|
|Subjects:||Chemistry, Organic chemistry|
|Keywords:||Diene, Hydrazone, Hypervalent iodide, Sigmatropic rearrangement|
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