Mechanistic Insights into Iron-Catalyzed Allenic C⁠–H Functionalization

Palermo, Philip (2023) Mechanistic Insights into Iron-Catalyzed Allenic C⁠–H Functionalization. Master's Thesis, University of Pittsburgh. (Unpublished)

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Abstract

The mechanism for the iron-catalyzed C–H functionalization of simple monosubstituted allenes is investigated. In this report, we determined that the mechanism of this transformation involves a deprotonation causing the organoiron species to transform from a datively bound η2-allene complex to a neutral η1-propargyliron complex. This iron species acts as a nucleophile for in-situ generated electrophiles, performing a SE2’ type reaction resulting in a disubstituted allene. Herein, we additionally discuss the subtle differences in ligand design and the ramifications on various reaction yields through analysis of electronic properties and x-ray structure.

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Details

Item Type:	University of Pittsburgh ETD
Status:	Unpublished
Creators/Authors:	Creators Email Pitt Username ORCID Palermo, Philip pnp13@pitt.edu pnp13 0009-0002-7309-694X
ETD Committee:	Title Member Email Address Pitt Username ORCID Thesis Advisor Wang, Yiming ym.wang@pitt.edu ymwang Committee Chair Transue, Wesley wtransue@pitt.edu wtransue Committee Chair Brummond, Kay kbrummon@pitt.edu kbrummon
Date:	10 May 2023
Date Type:	Publication
Defense Date:	30 March 2023
Approval Date:	10 May 2023
Submission Date:	16 March 2023
Access Restriction:	No restriction; Release the ETD for access worldwide immediately.
Number of Pages:	55
Institution:	University of Pittsburgh
Schools and Programs:	Dietrich School of Arts and Sciences > Chemistry
Degree:	MS - Master of Science
Thesis Type:	Master's Thesis
Refereed:	Yes
Uncontrolled Keywords:	Iron Catalysis Allene Transformation Iron Cyclopentadiene Piano stool complex
Date Deposited:	10 May 2023 18:57
Last Modified:	10 May 2023 18:57
URI:	http://d-scholarship.pitt.edu/id/eprint/44383

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• Mechanistic Insights into Iron-Catalyzed Allenic C⁠–H Functionalization. (deposited 10 May 2023 18:57) [Currently Displayed]

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