Journal article
Molecular recognition in asymmetric counteranion catalysis: understanding chiral phosphate-mediated desymmetrization
- Abstract:
- We describe the first theoretical study of a landmark example of chiral anion phase-transfer catalysis: the enantioselective ring-opening of meso-aziridinium and episulfonium cations promoted by asymmetric counteranion-directed catalysis (ACDC). The mechanism of ion-pairing, ring-opening, and catalyst deactivation have been studied in the condensed phase with both classical and quantum methods using explicitly and implicitly solvated models. We find that the stability of chiral ion-pairs, a prerequisite for asymmetric catalysis, is dominated by electrostatic interactions at long range and by CH···O interactions at short range. The decisive role of solvent upon ion-pair formation and of nonbonding interactions upon enantioselectivity are quantified by complementary computational approaches. The major enantiomer is favored by a smaller distortion of the substrate, demonstrated by a distortion/interaction analysis. Our computational results rationalize the stereoselectivity for several experimental results and demonstrate a combined classical/quantum approach to perform realistic modeling of chiral counterion catalysis in solution.
- Publication status:
- Published
- Peer review status:
- Peer reviewed
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- Files:
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(Preview, Accepted manuscript, pdf, 1.7MB, Terms of use)
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- Publisher copy:
- 10.1021/jacs.7b02468
Authors
- Publisher:
- American Chemical Society
- Journal:
- Journal of the American Chemical Society More from this journal
- Volume:
- 139
- Issue:
- 26
- Pages:
- 8886–8896
- Publication date:
- 2017-06-05
- Acceptance date:
- 2017-01-01
- DOI:
- EISSN:
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1520-5126
- ISSN:
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0002-7863
- Language:
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English
- Keywords:
- Pubs id:
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pubs:700813
- UUID:
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uuid:e17c9265-13c2-4ce7-8da7-66dc09fd2804
- Local pid:
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pubs:700813
- Source identifiers:
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700813
- Deposit date:
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2017-07-02
- ARK identifier:
Terms of use
- Copyright holder:
- American Chemical Society
- Copyright date:
- 2017
- Notes:
- Copyright © 2017 American Chemical Society. This is the accepted manuscript version of the article. The final version is available online from American Chemical Society at: https://doi.org/10.1021/jacs.7b02468
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