Scrivener, Sarah
(2024)
Iron-Catalyzed C–H Functionalization of Alkenes for Addition to Conjugated Electrophiles.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Allylic C(sp3)–H functionalization of simple alkenes, and subsequent coupling with Michael acceptors in a base metal catalyzed process offers a practical and modular approach to a variety of scaffolds. In this dissertation, the redox-neutral deprotonative generation of catalytic allyliron intermediates using a pentamethylcyclopentadienyliron(II) dicarbonyl catalyst provides an allyl anion equivalent for addition into α,β-unsaturated carbonyl derivatives. A wide range of alkene substrates serve as allyl pronucleophiles and undergo 1,4-conjugate addition to chalcone type electrophiles and other enones. Furthermore, Michael addition of alkenes to a collection of cyclic and acyclic nitrogen-containing compounds featuring C–C unsaturation, such as maleimides and enaminones, is also described. For some sterically hindered electrophiles, an alternative linear regioselectivity was observed. A preliminary investigation into the formation of these unexpected products is discussed.
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Details
Item Type: |
University of Pittsburgh ETD
|
Status: |
Unpublished |
Creators/Authors: |
|
ETD Committee: |
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Date: |
13 May 2024 |
Date Type: |
Publication |
Defense Date: |
28 March 2024 |
Approval Date: |
13 May 2024 |
Submission Date: |
7 March 2024 |
Access Restriction: |
2 year -- Restrict access to University of Pittsburgh for a period of 2 years. |
Number of Pages: |
503 |
Institution: |
University of Pittsburgh |
Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
Degree: |
PhD - Doctor of Philosophy |
Thesis Type: |
Doctoral Dissertation |
Refereed: |
Yes |
Uncontrolled Keywords: |
C–H Functionalization, Michael Addition, Iron |
Date Deposited: |
13 May 2024 13:56 |
Last Modified: |
13 May 2024 13:56 |
URI: |
http://d-scholarship.pitt.edu/id/eprint/45848 |
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