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Nickel-Catalyzed Regioselective Cross-Electrophile Alkene Difunctionalization

Quirion, Kevin (2023) Nickel-Catalyzed Regioselective Cross-Electrophile Alkene Difunctionalization. Master's Thesis, University of Pittsburgh. (Unpublished)

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Nickel-catalyzed alkene difunctionalization processes with two different carbon electrophiles can lead to the facile formation of many different types of C–C bonds. The use of two electrophiles with similar electronic properties is a unique application leading to regioselective bond formation utilizing commonly available and inexpensive alkyl and aryl iodides. To help explain this catalyst-controlled cross-electrophile selectivity, we utilize DFT calculations to examine the reaction mechanisms and the reactivity of aryl and alkyl iodide electrophiles in reactions with different nickel complexes. Specifically, several factors that control the reactivity of the oxidative addition with phenyl or n-butyl iodide are disclosed. First, the three-center cyclic oxidative addition transition states with Ni(0) complexes have a preferential reactivity with phenyl iodide in agreement with the experimental observations. The reaction of the resulting Ni(II) intermediate with the second electrophile takes place via the SN2-type oxidative addition of n-butyl iodide to the 4-coordinated Ni(II) complex. The origin of the lower activation energy of the SN2-type transition state compared to competing iodine atom transfer transition state was further examined using distortion/interaction analysis and the comparison of metal-to-electrophile charge transfer. A robust understanding for the factors promoting the cross-selectivity of aryl and alkyl iodides is important to expand the scope of the reaction and advance our understanding of nickel-catalyzed reactions.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Quirion, KevinKPQ1@pitt.eduKPQ1
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairLiu, Pengpengliu@pitt.edupengliu
Committee MemberWang,
Committee MemberFloreancig, Paulflorean@pitt.eduflorean
Date: 15 May 2023
Date Type: Publication
Defense Date: 17 September 2021
Approval Date: 15 May 2023
Submission Date: 5 April 2023
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 33
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: nickel catalysis
Date Deposited: 15 May 2023 19:59
Last Modified: 15 May 2023 19:59

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