Author ORCID Identifier
https://orcid.org/0000-0002-8915-2080
Date of Award
Summer 8-20-2026
Document Type
Thesis (Ph.D.)
Department or Program
Chemistry
First Advisor
David S. Glueck
Abstract
Chiral nitriles and amides are valuable in pharmaceuticals. A potentially useful approach to synthesize these functional groups is catalytic hydration of nitriles to yield amides; kinetic resolution of racemic nitriles with a chiral catalyst, the long-term goal of this research, could give both nitriles and amides in enantioenriched form. I investigated a class of platinum catalysts bearing hydroxyphosphine ligands, formed by tautomerization and coordination of secondary phosphine oxides (SPOs). Studies of the [Pt((R,R)-Me-FerroLANE)(PMe2OH)][OTf]2 catalyst precursor led to a proposed mechanism for nitrile hydration and identification of an iminol intermediate (Chapter 2). I synthesized SPO precursors bearing pendant amines, designed for intramolecular deprotonation of hydroxyphosphine ligands to yield hydrogen-bonded Pt-PR2(O)•••HNR3 groups (Chapters 3 and 5). Mechanistic studies of Pt catalysts with a P-stereogenic planar chiral hydroxyphosphine-amine resulted in evidence for inversion of configuration at phosphorus in nucleophilic ring opening of a metallacycle intermediate with water (Chapter 4).
Original Citation
Garduño, J. A.; Sasser, A. J.; Sexton, H. J.; Hughes, R. P.; Glueck, D. S.; Rheingold, A. L. Diastereoselective and Reversible Metallacycle Formation by Attack of a Pt-PR2OH Group on a Coordinated Nitrile in Pt-Catalyzed Hydration. Organometallics 2024, 43 (3), 381-394. DOI: 10.1021/acs.organomet.3c00483.
Recommended Citation
Sexton, Hannah J., "Nitrile Hydration Catalyzed by Chiral Pt-Hydroxyphosphine Complexes: Synthetic and Mechanistic Studies" (2026). Dartmouth College Ph.D Dissertations. 556.
https://digitalcommons.dartmouth.edu/dissertations/556
