Journal article

Publication year: 2015

Pages: 5748-5748

Journal: Journal of the American Chemical Society

Volume number: 137

Issue number: 17

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/jacs.5b00190

Publisher: American Chemical Society

Abstract: 

Racemic benzylic amines undergo kinetic resolution via benzoylation with
benzoic anhydride in the presence of a dual catalyst system consisting
of a readily available amide-thiourea catalyst and
4-dimethylaminopyridine (DMAP). An evaluation of various experimental
parameters was performed in order to derive a more detailed
understanding of what renders this process selective. The catalyst’s
aggregation behavior and anion-binding ability were evaluated in regard
to their relevance for the catalytic process. Alternate scenarios, such
as catalyst deprotonation or the in situ formation of a neutral chiral
acylating reagent were ruled out. Detailed computational studies at the
M06/6-31G(d,p) level of theory including solvent modeling utilizing a
polarized continuum model provide additional insights into the nature of
the ion pair and reveal a range of important secondary interactions
that are responsible for efficient enantiodiscrimination.

Harvard Citation style: Mittal, N., Lippert, K., De, C., Klauber, E., Emge, R., Schreiner, P., et al. (2015) A Dual-Catalysis Anion-Binding Approach to the Kinetic Resolution of Amines: Insights into the Mechanism via a Combined Experimental and Computational Study, Journal of the American Chemical Society, 137(17), p. 5748. https://doi.org/10.1021/jacs.5b00190

APA Citation style: Mittal, N., Lippert, K., De, C., Klauber, E., Emge, R., Schreiner, P., & Seidel, D. (2015). A Dual-Catalysis Anion-Binding Approach to the Kinetic Resolution of Amines: Insights into the Mechanism via a Combined Experimental and Computational Study. Journal of the American Chemical Society. 137(17), 5748. https://doi.org/10.1021/jacs.5b00190