Research Interests
Organic Molecules (Super Electron-Donors) in Electron Transfer Reactions
Simple organic compounds, in their neutral ground-state, can act as super-electron donors, where the transfer of electrons can initiate reactions. We now know that simple neutral organic molecules:
|
(i) can reduce aryl halides to organic radicals or organic anions, Angew. Chem. Int. Ed., 2007, 46, 5178-5183.
(ii) can reduce benzenes in the presence of malonates and cyanoacetates, J. Am. Chem. Soc., 2013, 135, 10934-10937.
|
More recently, many reactions have been discovered that lead to coupling of haloarenes to arenes, with the addition of base and an organic additive. A range of organic additives react with base to afford strong electron-donors in situ, initiating the base-induced homolytic aromatic substitution (BHAS) reaction, Chem. Sci., 2014, 5, 476-482
Grubbs-Stoltz Reducing System - KOtBu/Et3SiH Reagent Pair
The combination of potassium tert-butoxide and triethylsilane affords a range of distinctive reaction types. These arise through the many reactive intermediates, some of which are competitive, Chem. Sci., 2020, 26, 12364 - 1370. Additionally, our investigations in this area have shown that:
|
i) the range of mechanisms available to the reagent pair include electron transfer and hydride delivery to arenes, Angew. Chem. Int. Ed., 2017, 56, 13747.
ii) A range of substrates undergo radical-based rearrangements to afford new compounds. Indoles rearrange to dihydroacridines, Chem. Sci., 2020, 11, 3719-3726
- ortho-Tolyl aryl ethers rearrange to substituted diphenylmethanes, Adv. Synth. Catal., 2020, 362, 2260-2267, as well as amines and sulfides. This was recently extended to tertiary amine substrates, Molecules, 2021, 26, 6879
|
