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Efforts Towards C-C Bond Formations: From Ni Catalysis to Transition-Metal Free Electrolysis


Zhang, Wanji Wendy (2024) Efforts Towards C-C Bond Formations: From Ni Catalysis to Transition-Metal Free Electrolysis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/czam-9x35.


The selective construction of C-C bonds has been a critical challenge in modern synthetic organic chemistry. Among the numerous methodologies developed, cross-coupling remains an attractive strategy for direct C-C bond formation. Herein, a diverse range of cross-coupling reactions for C-C bond formations are investigated from different perspectives. First, the mechanism of a Ni/cyano-box-catalyzed asymmetric Suzuki alkynylation is studied. The existing data is consistent with a radical chain pathway that is previously proposed for other Ni-catalyzed enantioselective cross-coupling reactions. Next, moving on from the traditional electrophile-nucleophile cross-couplings, we explore Ni-catalyzed reductive coupling of alkyl halides with internal olefins in the presence of a hydrosilane. With judicious choice of the directing group, hydroalkylation of internal olefins can be achieved with high regio- and enantioselectivity. Following that, an electrochemically driven, transition-metal free cross-electrophile coupling reaction is explored as a greener alternative to constructive C(sp³)-C(sp³) bonds. Specifically, we focus on improving the Mg sacrificial anode performance in these electroreductive systems. By carefully choosing the electrolyte composition, we are able to manipulate the metal electrode interfaces for a more effective counter electrode. Finally, Al stripping in ethereal solvents is investigated for its application as a sacrificial anode in reductive electrosynthesis. Inspired by Al corrosion chemistry, we are able to achieve bulk Al stripping in THF-based electrolyte by incorporating halide co-supporting electrolytes.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:nickel catalysis; mechanistic investigation; methodology; sacrificial anode; Mg passivation; Mg stripping; Al passivation; Al stripping; tetrahydrofuran-based electrolyte; reductive electrosynthesis
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • See, Kimberly A.
Thesis Committee:
  • Reisman, Sarah E. (chair)
  • Stoltz, Brian M.
  • Fu, Gregory C.
  • See, Kimberly
Defense Date:19 July 2023
Record Number:CaltechTHESIS:08212023-202451948
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 3
Zhang, Wanji Wendy0000-0002-6895-9598
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16161
Deposited By: Wanji Zhang
Deposited On:09 Oct 2023 22:34
Last Modified:29 May 2024 19:30

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