Dissertation/Thesis Abstract

Development of N-Allylhydrazone-Based Transformations
by Mundal, Devon Allen, Ph.D., Northwestern University, 2011, 270; 3489370
Abstract (Summary)

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.

Indexing (document details)
Advisor: Thomson, Regan J.
Commitee: Silverman, Richard B., Sonbinh, Nguyen T.
School: Northwestern University
Department: Chemistry
School Location: United States -- Illinois
Source: DAI-B 73/04, Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Organic chemistry
Keywords: Hydrazone, N-allylhydrazone, Petasis, Sigmatropic rearrangement, Traceless, Transformations
Publication Number: 3489370
ISBN: 978-1-267-08613-6
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