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Computational Study on Site-Selectivity of DMDO-Mediated C–H Hydroxylation

Chen, Yimin (2024) Computational Study on Site-Selectivity of DMDO-Mediated C–H Hydroxylation. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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C–H hydroxylation is an important type of transformation in organic synthesis. However, it is challenging to control the site-selectivity for structurally complex substrates with multiple C–H bonds of similar inherent reactivities. The site-selectivity of dimethyldioxirane (DMDO)-mediated C–H hydroxylation is investigated via computational chemistry tools and statistical methods to better understand factors affecting site-selectivity and to develop a predictive model for site-selectivity. In addition to the previously recognized electronic effects on site-selectivity, this study reveals the significance of steric effects and strain-release effects. A model capable of quantifying the electronic effects, steric effects, and strain-release effects on the selectivity of structurally complex compounds is developed. A reaction-specific descriptor based on solvent-accessible surface area (SASA) is developed to describe steric effects of C–H bonds. An activation function was found to be critical to improve the performance of the SASA descriptor. In addition, further application of the site-selectivity prediction model to a macrocyclic molecule is performed to examine the applicability of the model to structurally complex and conformationally flexible molecules.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Chen, Yiminyic109@pitt.eduyic1090000-0002-4818-5038
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee MemberFloreancig, Paulflorean@pitt.eduflorean
Committee MemberCoalson, Rob Duncancoalson@pitt.educoalson
Committee MemberKeith, John Andrewjakeith@pitt.edujakeith
Committee ChairLiu, Pengpengliu@pitt.edupengliu0000-0002-8188-632X
Date: 10 January 2024
Date Type: Publication
Defense Date: 17 August 2023
Approval Date: 10 January 2024
Submission Date: 16 August 2023
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 152
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: DMDO, hydroxylation, predictive model, C–H activation, descriptor, steric effects
Date Deposited: 10 Jan 2024 14:50
Last Modified: 10 Jan 2024 14:50

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  • Computational Study on Site-Selectivity of DMDO-Mediated C–H Hydroxylation. (deposited 10 Jan 2024 14:50) [Currently Displayed]


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