Chemistry and Biochemistry
Mitsunobu Reaction, Organocatalyst, Elimination-addition, Addition-rearrangement, Redox-neutral, Computational, Secondary Phosphine Oxides
The purpose of this thesis was the identification of a more efficient catalyst analog that could perform the redox-neutral Mitsunobu reaction, which was achieved via two synthetic pathways: elimination-addition and addition-rearrangement. Furthermore, a computational investigation was conducted on the conflicting interpretations of the catalytic cycle. Our research group replicated Houk et al. work, as well as expanded the computations to examine the influence different functional groups had on the ground state and transition state structures. Important ground state and transition state structures were determined, which provided a more energetically favorable pathway of the catalytic cycle. Experimental work demonstrated that both one-step syntheses could generate modified organocatalyst and observe the influence different functional groups had on the catalytic activity. The addition-rearrangement synthesis was determined to be the optimal pathway with yields ≥ 70%.
Brown, S. (2021). Computational and Experimental Studies of Functionalized Phenolic Tertiary Phosphine Oxides as Organocatalysts for the Redox-Neutral Mitsunobu Reaction (Master's thesis, Duquesne University). Retrieved from https://dsc.duq.edu/etd/1965