Graduate Student Scott Shreiber

"Enabling Fluoroalkylations with Nickel"

The incorporation of fluorine into organic molecules is well-known to alter various chemical and physical properties that are important to a variety of fields. The industrial significance of fluorination is evidenced by the fact that over 50% of new agrochemicals in the past twenty years contain fluorine.1 Similarly, over 40% of new small molecule pharmaceuticals introduced to the market in 2018 and 2019 contain fluorine.2 However, methods for incorporating even small fluorine-containing functionalities has remained challenging. Our group has recently focused our attention on developing fluoroalkylation chemistries with base metals such as copper3, cobalt4-6, and nickel7-10. In this seminar, I will present my recent efforts to develop new methodologies using highly fluoroalkylated nickelate complexes that are chemically ligated only by solvent molecules. These easily oxidizable simple nickel salts are successful in performing stoichiometric and catalytic fluoroalkylations of organic substrates. Methods to derivatize these simple nickel salts for tailored chemistries will be presented, as will the use of the nickel salts to perform stereoselective transformations of natural products.

1) Ogawa, Y.; Tokunaga, E.; Kobayashi, O.; Hirai, K.; Shibata, N. iScience 2020, 23, 101467.
2) Inoue, M.; Sumii, Y.; Shibata, N. ACS Omega 2020, 5, 10633.
3) Shreiber, S.T.; Kaplan, P.T.; Hughes, R. P.; Vasiliu, M.; Dixon, D.A.; Cramer, R. E.; Vicic, D.A. J. Fluorine Chem. 2020, 234, 109518.
4) Shreiber, S.T.; Scudder, J.J.; Vicic, D.A. Organometallics 2019, 38, 3169.
5) Shreiber, S.T.; Vicic, D.A. Helv. Chim. Acta. 2020, 103, e20000149.
6) Shreiber, S. T.; Vicic, D.A. J. Organomet. Chem. 2021, 949, 121974.
7) Shreiber, S.T.; DiMucci, I.M.; Khrizanforov, M.N.; Titus, C.J.; Nordlund, D.; Dudkina, Y.; Cramer, R.E.; Budnikova, Y.; Lancaster, K.M.; Vicic, D.A. Inorg. Chem. 2020, 59, 9143.
8) Shreiber, S.T.; Vicic, D.A. Angew. Chem. Int. Ed. 2021, 60, 18162.
9) Shreiber, S.T.; Puchall, G.I.; Vicic, D.A. 2022, manuscript in preparation.
10) Shreiber, S.T.; Amin, F.; Cramer, R.E.; Vicic, D.A. 2022, manuscript in preparation.