Link to the University of Pittsburgh Homepage
Link to the University Library System Homepage Link to the Contact Us Form
D-Scholarship @ Pitt Banner and Links to Homepage

Computational Study of the Impacts of Directing Group and Ligand Flexibility in Directed Alkene Functionalization

Alturaifi, Turki (2023) Computational Study of the Impacts of Directing Group and Ligand Flexibility in Directed Alkene Functionalization. Master's Thesis, University of Pittsburgh. (Unpublished)

This is the latest version of this item.

[img] PDF
Restricted to University of Pittsburgh users only until 6 September 2024.
Download (2MB) | Request a Copy

Abstract

This computational study investigates the roles of flexible ligands and directing groups in Ni- and Pd-catalyzed alkene functionalization reactions. Many hemilabile and conformationally flexible ligands and directing groups have been employed in these catalytic transformations, where the ligands (e.g., bioxazolines and quinones) may adopt different binding modes and the chelating directing groups may have different ring-flip conformations. However, the effects of flexibility on reactivity and selectivity are still not well understood. Here, we examine the flexibility effects in three catalytic reactions, including the binding modes of quinone-type ligands in Ni-catalyzed 1,2-carbosulfenylation of unactivated alkenes, the coordination modes of bioxazoline-based ligands in Ni-catalyzed asymmetric 1,2-diarylation of unactivated alkenes, and the effectiveness of L-tert-leucine as a transient directing group (TDG) in controlling enantioselectivity in Heck-reductive hydrofunctionalization. We show that the duroquinone (DQ) ligand adopts different binding modes in different elementary steps of the Ni-catalyzed 1,2-carbosulfenylation—it binds as an X-type redox-active durosemiquinone (DSQ) radical anion to promote alkene migratory insertion with a less distorted square planar Ni(II) center, whereas it binds as an L-type ligand to promote oxidative addition at a more electron-rich Ni(I) center. We found that in different elementary steps of the catalytic cycle of the Ni-catalyzed alkene diarylation, the bioxazoline ligand can be bidentate, monodentate, or completely dissociated depending on the steric and electronic properties of the transition state. The enantioselectivity-determining step involves a square planar Ni(II) migratory insertion transition state, stabilized by non-covalent interactions with a dissociated arm of the bioxazoline ligand. Finally, we show how the rigidity of the bidentately bounded chiral amino acid TDGs, induced by their α-substituent, promote binding of the TDG and induce high levels of enantioselectivity in alkene insertion with a variety of migrating groups in the reductive-Heck hydrofunctionalization.

Share

Citation/Export:
Social Networking:
Share |

Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Alturaifi, Turkitma53@pitt.edutma53@pitt.edu
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee MemberBrummond, Kaykbrummon@pitt.edukbrummon
Committee MemberKazunori, Koidekoide@pitt.edukoide
Thesis AdvisorLiu, Pengpengliu@pitt.edupengliu
Date: 6 September 2023
Date Type: Publication
Defense Date: 2 May 2023
Approval Date: 6 September 2023
Submission Date: 3 August 2023
Access Restriction: 1 year -- Restrict access to University of Pittsburgh for a period of 1 year.
Number of Pages: 37
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: Flexibility, alkene functionalization, asymmetric catalysis
Date Deposited: 07 Sep 2023 01:38
Last Modified: 07 Sep 2023 01:38
URI: http://d-scholarship.pitt.edu/id/eprint/45271

Available Versions of this Item

Metrics

Monthly Views for the past 3 years

Plum Analytics

Actions (login required)

View Item View Item