The [3,3]-sigmatropic rearrangement of N-allylhydrazones is a potentially powerful, yet under-explored reaction that forges a new carbon–carbon bond while generating a labile monoalkyldiazine intermediate. Subsequent loss of dinitrogen affords a product containing no trace of the original hydrazone functionality. Our efforts to render the [3,3]-sigmatropic rearrangement of N-allylhydrazones a reliable traceless fragment coupling reaction have led to the discovery and development of several novel N-allylhydrazone-based transformations.
Early investigations unearthed a copper(II) chloride-promoted tandem carbon–carbon and carbon–chlorine bond forming [3,3]-sigmatropic rearrangement of N-allylhydrazones. This discovery led to the development of a reliable method for the synthesis of homoallylic chlorides. Extension of this reactivity to include tandem carbon–carbon and carbon–bromine bond formation allowed for the development of a stereoselective, hydrazone-based synthesis of dienes.
In line with our initial goal, efforts toward an N-allyhydrazone-based traceless fragment coupling led to the discovery and development of a triflimide-catalyzed [3,3]-sigmatropic rearrangement of N-allylhydrazones.
Finally, further studies in the area of hydrazone-based traceless fragment coupling reactions have led to the development of a traceless Petasis–Mannich reaction for the synthesis of allenes.
|Advisor:||Thomson, Regan J.|
|Commitee:||Silverman, Richard B., Sonbinh, Nguyen T.|
|School Location:||United States -- Illinois|
|Source:||DAI-B 73/04, Dissertation Abstracts International|
|Keywords:||Hydrazone, N-allylhydrazone, Petasis, Sigmatropic rearrangement, Traceless, Transformations|
Copyright in each Dissertation and Thesis is retained by the author. All Rights Reserved
The supplemental file or files you are about to download were provided to ProQuest by the author as part of a
dissertation or thesis. The supplemental files are provided "AS IS" without warranty. ProQuest is not responsible for the
content, format or impact on the supplemental file(s) on our system. in some cases, the file type may be unknown or
may be a .exe file. We recommend caution as you open such files.
Copyright of the original materials contained in the supplemental file is retained by the author and your access to the
supplemental files is subject to the ProQuest Terms and Conditions of use.
Depending on the size of the file(s) you are downloading, the system may take some time to download them. Please be