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Organic Chemistry

Assistant Professor

Education
Contact Information

Research Interests

Our group is interested in the chemistry of reactive intermediates. These are species that are formed during the course of a chemical reaction, and are responsible for chemical reactivity. Depending on the nature of the intermediate, these species have lifetimes ranging from thousandths to billionths of a second. We use a number of techniques from standard analytical methods (like NMR, GC and HPLC) to highly specialized methods such as laser flash photolysis (LFP), and high level computational methods, to understand the structures and reactivity of these short-lived species. The types of compounds we investigate are quite varied:

Free Radicals. These are organic species which contain a single unpaired electron in their valence shell. In particular, carbon centered free radicals are important intermediates in polymerization reactions. Presently we are investigating the chemistry of 3-phenylpropyl radical systems; specifically their potential to fragment to yield benzylic radicals, and their potential to cyclize (under oxidizing conditions), to yield indane species. The effect of functionalization on the degree of competition between fragmentation, cyclization and coupling is being investigated.

Carbenes and Nitrenes. These are species that have only six electrons in the valence shell of carbon or nitrogen respectively, and are thus highly reactive. Phenylnitrene, for example, exhibits interesting chemistry in solution, as it may rearrange through a series of highly strained intermediates:

formation of nitrenes graphic

We are currently investigating the effect of changing the structure of this species, either on or within the ring, on the reactivity of the nitrene. In addition, the precursors of the species, aromatic azides, are known to undergo 1,3-dipolar cycloaddition reactions with alkenes and alkynes. The effect of functionality on the outcome of these reactions is also being investigated.

Reactive Oxygen Species (ROS). ROS is something of a catchall term for a range of reactive intermediates. The only thing they have in common is that their reactive centers involve oxygen in some form or another. These species are known to be important in a range of biological processes: from beneficial processes such as metabolism, to less beneficial processes such as carcinogenesis. In addition, these species are presumed to play an important role in environmental processes, including the breakdown of persistent pollutants both in the atmosphere and the hydrosphere. We are developing novel analytical techniques to measure the reactivity of these species in aqueous and non-aqueous environments.

Publications

  1. Hostetler, K.J.; Crabtree, K.N.; Poole, J.S.* "The Photochemistry of 4-Azidopyridine-1-Oxide", J. Org. Chem., 2006, 71, 9023-9029.

  2. Hostetler, K.J.; Poole, J.S.; Fanwick, P.E.* "N'-[5'-(3',5'-dimethoxycarbonyl-2'-pyrazolinyl)]methyl- 4-aminopyridine-1-oxide monohydrate" Acta Cryst., Sect. E., 2006, E62, o3015-3016.

  3. Yonekawa, S.; Goodpaster, A.M.; Abel, B.A.; Paulin, R.G.; Sexton, C.W.; Poole, J.S.; Storhoff, B.N.*; Fanwick, P.E. "Synthesis, Properties and X-ray Structure of 5-Azido-2-methoxy-1,3-xylyl-18-crown-5", J. Heterocyclic Chem. 2006, 43, 689-694

  4. DeMatteo, M; Poole, J S; Shi, X; Sachdeva, R; Hatcher, P G; Hadad, C M;* Platz, M S;* "On the Electrophilicity of Hydroxyl Radical: A Laser Flash Photolysis and Computational Study." J. Am. Chem. Soc. 2005, 127, 7094-7109.

  5. Poole, J S;* Shi, X; Hadad, C M;* Platz, M S;* "Reaction of Hydroxyl Radical with Aromatic Hydrocarbons in Non-Aqueous Solutions — a Laser Flash Photolysis Study in Acetonitrile." J. Phys. Chem. A. 2005, 109, 2547-2551.

  6. Beckwith, A L J; Poole, J S.* "Factors Affecting the Rates of Addition of Free Radicals to Alkenes-Determination of Absolute Rate Coefficients Using the Persistent Aminoxyl Method." J. Am. Chem. Soc. 2002; 123, 9489-9497.

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