HARNESSING THE CHEMISTRY OF CO2
Our research program is broadly focused on activating CO{sub 2} through the use of organic and organometallic based catalysts. Some of our methods have centered on annulation reactions of unsaturated hydrocarbons (and carbonyl substrates) to provide a diverse array of carbocycles and heterocycles. We use a combination of catalyst discovery and optimization in conjunction with classical physical organic chemistry to elucidate the key mechanistic features of the cycloaddition reactions such that the next big advances in catalyst development can be made. Key to all of our cycloaddition reactions is the use of a sterically hindered, electron donating N heterocyclic carbene (NHC) ligand, namely IPr (or SIPr), in conjunction with a low valent nickel pre-catalyst. The efficacy of this ligand is two-fold: (1) the high {delta}-donating ability of the NHC increases the nucleophilicity of the metal center which thereby facilitates interaction with the electrophilic carbonyl and (2) the steric hindrance prevents an otherwise competitive side reaction involving only the alkyne substrate. Such a system has allowed for the facile cycloaddition to prepare highly functionalized pyrones, pyridones, pyrans, as well as novel carbocycles. Importantly, all reactions proceed under extremely mild conditions (room temperature, atmospheric pressures, and short reaction times), require only catalytic amounts of Ni/NHC and readily available starting materials, and afford annulated products in excellent yields. Our current focus revolves around understanding the fundamental processes that govern these cycloadditions such that the next big advance in the cyclization chemistry of CO{sub 2} can be made. Concurrent to our annulation chemistry is our investigation of the potential for imidazolylidenes to function as thermally-actuated CO{sub 2} sequestering and delivery agents.
- Research Organization:
- Univ. of Utah, Salt Lake City, UT (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- FG02-05ER15689
- OSTI ID:
- 978850
- Report Number(s):
- DOE/ER/15689; 55800454; TRN: US201202%%805
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis and properties of heterofulvenes. Derivatives of 2,6-dimethyl-.gamma.-pyrone, -.gamma.-thiapyrone, and N-butyl-2,6-dimethyl-.gamma.-pyridone
Insertion reactions and structural studies of [(NHC)CuH]2 with nitrogen-based substrates