Research | gearylab

Broad Research Objectives

We have two broad synthetic objectives - to develop robust and chemoselective catalytic methods for C-C and C-X bond formation, and to develop methods that synthesize small molecules to address biological problems.

We use both transition metal catalysis and Lewis acid catalysis to enable bond formation. In addition to method development, we are also interested in studying the mechanisms of reactions using in situ FTIR spectroscopy and XAS.

We collaborate with Jason Shearer (Trinity Univesrsity) on XAS, Matthew Tucker (UNR chemistry) on photoswitchable surfactants, Brian Frost (UNR chemistry) for X-ray crystallography, and Andy Tennyson (Clemson) on the application of PKR adducts in synthesis.

Pauson-Khand Reaction

The Pauson-Khand reaction is a [2+2+1] cycloaddition that couples an alkyne, alkene and carbon monoxide to generate 3 new C-C bonds and furnish a cyclopentenone. Our interests in the PKR are both synthetic and mechanistic.

Though known for more than 40 years, there are a number of synthetic limitations. Insertion of the alkyne component is completely selective for the substituent to incorporate at the alpha position; if a disubstituted alkyne is used, mixtures usually ensue. We have identified simple, inexpensive alkynes to address that. We are also developing new chemistry that will allow the incorporation of alpha-olefins in an intermolecular PKR for the first time! Typical PKR chemistry is mediated by N-oxides, and we are developing alternates to the currently used oxides, as well alternates to CO gas.

Our collaboration with the Shearer group is on the characterization of the organocobalt intermediates, and we're also developing chemistry that avoids typical norbornenes in the reaction.

Thanks to the NIH-NIGMS (R15GM120738) and the NSF (CAREER 1753098) for funding some of this work!

Catalytic Olefination

The Wittig reaction was discovered over 60 years ago, yet remains one of the most common methods to synthesized C=C double bonds on small scales. However, the stoichiometric generation of phosphine oxide waste has greatly limited the application of the Wittig reaction on more substantial scales.

We are interested in developing a catalytic method that uses a simple oxygen sink to enable the C=C bond formation. Some of our preliminary data related to a stoichiometric method were published recently, and our first paper on a catalytic variant should be in print not too long from now!

Thanks to the NSF Chemical Catalysis for funding some of this work! (CAREER 1753098)

N-Oxides in Synthesis

Our recent work with nitrous oxide in Pauson-Khand chemistry has led us to explore nitrous oxide in other reactions, as well as the application and study of other N-oxides in synthesis. Stay tuned for results in those areas!