Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 38, Pages 15433-15440Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b08185
Keywords
-
Categories
Funding
- National Institutes of Health (National Institute of General Medical Sciences) [R01-GM062871]
- Dow Next Generation Educator Fund
Ask authors/readers for more resources
In recent years, a wide array of methods for achieving nickel-catalyzed substitution reactions of alkyl electrophiles by organometallic nucleophiles, including enantioconvergent processes, have been described; however, experiment-focused mechanistic studies of such couplings have been comparatively scarce. The most detailed mechanistic investigations to date have examined catalysts that bear tridentate ligands and, with one exception, processes that are not enantioselective; studies of catalysts based on bidentate ligands could be anticipated to be more challenging, due to difficulty in isolating proposed intermediates as a result of instability arising from coordinative unsaturation. In this investigation, we explore the mechanism of enantioconvergent Kumada reactions of racemic alpha-bromoketones catalyzed by a nickel complex that bears a bidentate chiral bis(oxazoline) ligand. Utilizing an array of mechanistic tools (including isolation and reactivity studies of three of the four proposed nickel-containing intermediates, as well as interrogation via EPR spectroscopy, UV-vis spectroscopy, radical probes, and DFT calculations), we provide support for a pathway in which carbon-carbon bond formation proceeds via a radical-chain process wherein a nickel(I) complex serves as the chain-carrying radical and an organonickel(II) complex is the predominant resting state of the catalyst. Computations indicate that the coupling of this organonickel(II) complex with an organic radical is the stereochemistry-determining step of the reaction.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available