Faculty Research
Examples of ongoing projects include:
Development of New Silicon-Based Synthetic Transformations: Our group has developed several new reactions that harness the unique reactivity of silicon to synthesize valuable compounds that would otherwise be difficult to prepare. These include:
(1) Iodine-Promoted Rearrangements of Diallylsilanes: Treatment of diallylsilanes with iodine results in a carbon-carbon bond forming rearrangement, leading to useful synthetic intermediates from readily available staring materials. Most recently this strategy was used to prepare complex organosilanes containing a stereogenic silicon atom. Compounds of this type are of interest within the fields of materials science and medicinal chemistry:
- See: Tan, Elliott D.; Wier, K. E.; O'Neil, G. W.* "Iodine Rearrangements of Tetraallylsilane and Synthesis of Silicon-Stereogenic Organosilanes" Int. J. Mol. Sci. 2024, 25, 9996 (Special Issue: New Horizons in Silicon Chemistry).
(2) Hydrosilylation Reactions: The hydrosilylation reaction is a fundamental process in organosilicon chemistry, widely implemented to produce valuable organosilanes, for instance as intermediates in the synthesis of pharmaceuticals and polymers. Our group has introduced several new hydrosilylation protocols, most recently to produce valuable silicon and oxygen-containing ring systems:
- See: Peterson, H. J.; O'Neil, G. W.* "TBAT-catalyzed dioxasilinane formation from beta-hydroxy ketones" Tetrahedron 2025, 171, 134418.
- See: Billmire, T.Q.; Jones, A. P.; Maffett, S. M.; Gervais, C.; Kaminsky, W. O'Neil, G. W.* Synthesis of Oxasilolanes by TBAT-Catalyzed Hydroxyl-Directed Hydrosilylation. J. Org. Chem. 2025 ASAP.
New Reactions Employing Samarium(II). Samarium(II) reagents can act as single electron transfer (SET) agents, triggering various chemical reactions. Our group is working on developing new methods that begin with SET from samarium(II) to synthesize complex and valuable organic molecules. One recent example involves reductions of sulfone-containing structures to generate allylic alcohol products with complete control of their three-dimensional shape:
- See: Schwans, C. L.; Clark, T. D.; O'Neil, G. W.* "Hydroxyl-Directed Regio- and Diastereoselective Allylic Sulfone Reductions with [Sm(H2O)n]I2" J. Org. Chem. 2024, 89, 692-700.
Microalgal alkenones: Long-chain alkenones are a unique class of lipids biosynthesized by several haptophyte algae. Alkenone structures are characterized by long hydrocarbon chains (C35 - C40) containing trans-double bonds separated by five methylenes and terminating in a methyl or ethyl ketone. We continue to investigate alkenones as a renewable hydrocarbon feedstock for use across various industries. Most recently that has involved tracking changes to alkenone structure and yield in industrially produced algae:
- See: O'Neil, G. W.*, Keller, A.; Balila, J.; Golden, S.; Sipila, N.; Stone, B.; Nelson, R. K.; Reddy, C. M. "Monitoring Changes to Alkenone Biosynthesis in Commercial Tisochrysis lutea Microalgae" ACS Omega 2024, 9, 16374-16383.