Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 80, Issue 7, Pages 3597-3610Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.5b00301
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- Government of Saskatchewan for an Innovation and Opportunity Scholarship
- Natural Sciences and Engineering Research Council of Canada
- Canada Foundation for Innovation
- Universite de Sherbrooke
- University of Saskatchewan
- WestGrid
- Compute Canada Calcul Canada
- Calcul Quebec
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An exploration into the origin of chemoselectivity in the NHC-catalyzed cross-benzoin reaction reveals several key factors governing the preferred pathway. In the first computational study to explore the cross-benzoin reaction, a piperidinone-derived triazolium catalyst produces kinetically controlled chemoselectivity. This is supported by H-1 NMR studies as well as a series of crossover experiments. Major contributors include the rapid and preferential formation of an NHC adduct with alkyl aldehydes, a rate-limiting carbon-carbon bond formation step benefiting from a stabilizing pi-stacking/pi-cation interaction, and steric penalties paid by competing pathways. The energy profile for the analogous pyrrolidinone-derived catalyst was found to be remarkably similar, despite experimental data showing that it is less chemoselective. The chemoselectivity could not be improved through kinetic control; however, equilibrating conditions show substantial preference for the same cross-benzoin product kinetically favored by the piperidinone-derived catalyst.
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