Research

We are a young research group that is applying “systems” and supramolecular ways of thinking to solve problems in catalysis as it relates to organic chemistry and the chemical origins of life. Interrelated areas of focus include:

1) Aggregation in Brønsted acid catalysis

We have uncovered some interesting solvent effects that push the boundaries of known reactivity of Brønsted acid catalysis. Mechanistic experiments suggest that the formation of higher order aggregates involving solvents such as nitromethane and hexafluoroisopropanol are critical to the observed reactivity. We are working to deepen our understanding of these phenomena and continue to exploit them to develop methods of interest for organic synthesis, such as the direct nucleophilic substitution of alcohols [1][2] or alkyl fluorides [3] and the ring opening of cyclopropanes [4].

[1] (a) Angew. Chem. Int. Ed. 2017, 56, 3085. (b)  J. Am. Chem. Soc. 2015, 137, 9555. (c) Org. Biomol. Chem. 2014, 12, 5990. [2] For our review of catalytic dehydrative alcohol substitution, see Synthesis 2016, 48, 935. [3] (a) ACS Catalysis 2016, 6, 3670. (b)  J. Fluor. Chem. 2017, 193, 45. [4] (a) Org. Lett. 2018, 20, 574. (b) Chem. Sci. 20189, 6411.

2) Catalyst discovery using complex mixtures – a systems approach

toc-synpacts

We have developed a simple algorithmic approach for screening and deconvoluting complex mixtures of catalyst components with the goal of rapidly identifying new catalysts and cooperative effects.[1] We have used this strategy to uncover new organoboron [2] and nickel [2][3] catalysts, and have found that catalysts selected in this way tend to be useful in multicatalysis.[4] The continuing goal of this project is to discover new  cooperative effects and multicatalytic processes.

[1] For an account of our recent work in this area, see: Synlett 2016, 27, 2637. [2] Chem. Sci. 2015, 6, 2501. [3] J. Org. Chem. 2015, 80, 6922. [4] Chem. Eur. J. 2016, 22, 12274.

3) Self-organized reaction networks to understand the origin of life

metabolism

How did life’s chemical pathways emerge before there were enzymes to act as catalysts? Why does biochemistry use the reactions and pathways that it does and not others? This ERC-funded project aims to understand  the prebiotic origins of biological metabolism. In the first phase of the project, we experimentally investigated the possibility that core biological anabolic pathways present in early life may have originated as non-enzymatic chemistry, including the acetyl CoA pathway [1] and the reverse Krebs cycle [2]. Now in the second phase of the project, we are exploring reaction networks that could have been precursors to metabolic cycles, such as the Krebs and glyoxylate cycles [3]. Our results suggest that certain ancient biochemical pathways were outgrowths of geochemistry. For an overview, see below for Joseph’s short talk from the 2018 ACS meeting in Boston.

[1] Nature Ecol. Evol. 2018, 2, 1019-1024. [2] Nature Ecol. Evol. 2017, 1, 1716-1721. [3] ChemRxiv 2018, doi: 10.26434/chemrxiv.7178930.v1.

4) Vibrational Strong Coupling for organic chemistry and catalysis

TOC graphic

This project aims to develop a completely new way to control the rate and selectivity of organic reactions: by selectively modifying the molecular vibrations involved in a reaction simply by running them in an appropriately-sized reaction vessel. It might sound like magic, but Vibrational Strong Coupling (VSC) is an emerging field in the quantum optics community. A collaboration between our group and the group of Prof. Thomas Ebbesen, a world leader in VSC, aims to exploit this phenomenon for use in organic synthesis and catalysis. Thus far, we have shown that VSC can be used to change the rates of ground state organic reactions.[1] Ongoing work aims to use VSC to modulate selectivity, to understand which functional groups and reaction mechanisms are most susceptible to VSC, as well as to explore the effect of VSC on catalysis.

[1] Angew. Chem. Int. Ed. 2016, 55, 11462.

For more information on ongoing projects, please contact Dr. Moran directly.