The DOI matches its Crossref record.
On the Theory of Organic Catalysis “on Water”
Abstract
A molecular origin of the striking rate increase observed in a reaction on water is studied theoretically. A key aspect of the on-water rate phenomenon is the chemistry between water and reactants that occurs at an oil-water phase boundary. In particular, the structure of water at the oil-water interface of an oil emulsion, in which approximately one in every four interfacial water molecules has a free ("dangling") OH group that protrudes into the organic phase, plays a key role in catalyzing reactions via the formation of hydrogen bonds. Catalysis is expected when these OH's form stronger hydrogen bonds with the transition state than with the reactants. In experiments more than a 5 orders of magnitude enhancement in rate constant was found in a chosen reaction. The structural arrangement at the "oil-water" interface is in contrast to the structure of water molecules around a small hydrophobic solute in homogeneous solution, where the water molecules are tangentially oriented. The latter implies that a breaking of an existing hydrogen-bond network in homogeneous solution is needed in order to permit a catalytic effect of hydrogen bonds, but not for the on-water reaction. Thereby, the reaction in homogeneous aqueous solution is intrinsically slower than the surface reaction, as observed experimentally. The proposed mechanism of rate acceleration is discussed in light of other on-water reactions that showed smaller accelerations in rates. To interpret the results in different media, a method is given for comparing the rate constants of different rate processes, homogeneous, neat and on-water, all of which have different units, by introducing models that reduce them to the same units. The observed deuterium kinetic isotope effect is discussed briefly, and some experiments are suggested that can test the present interpretation and increase our understanding of the on-water catalysis.
Overview
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Verification
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Citations
Cited by
Deep eutectic solvents: syntheses, properties and applications
Zhang, Q., De Oliveira Vigier, K., Royer, S., & Jérôme, F. (2012) · Chemical Society Reviews · doi:10.1039/c2cs35178a · Cited by 4,899
Chanda, A., & Fokin, V. V. (2009) · Chemical Reviews · doi:10.1021/cr800448q · Cited by 1,534
Butler, R. N., & Coyne, A. G. (2010) · Chemical Reviews · doi:10.1021/cr100162c · Cited by 1,108
Supramolecular catalysis. Part 2: artificial enzyme mimics
Raynal, M., Ballester, P., Vidal-Ferran, A., & van Leeuwen, P. W. N. M. (2014) · Chem. Soc. Rev. · doi:10.1039/c3cs60037h · Cited by 927
Mellmann, D., Sponholz, P., Junge, H., & Beller, M. (2016) · Chemical Society Reviews · doi:10.1039/c5cs00618j · Cited by 872
Raynal, M., Ballester, P., Vidal-Ferran, A., & van Leeuwen, P. W. N. M. (2014) · Chem. Soc. Rev. · doi:10.1039/c3cs60027k · Cited by 717
Interface-Assisted Synthesis of 2D Materials: Trend and Challenges
Dong, R., Zhang, T., & Feng, X. (2018) · Chemical Reviews · doi:10.1021/acs.chemrev.8b00056 · Cited by 710
Benign by design: catalyst-free in-water, on-water green chemical methodologies in organic synthesis
Gawande, M. B., Bonifácio, V. D. B., Luque, R., Branco, P. S., & Varma, R. S. (2013) · Chemical Society Reviews · doi:10.1039/c3cs60025d · Cited by 674
Tetrazoles via Multicomponent Reactions
Neochoritis, C. G., Zhao, T., & Dömling, A. (2019) · Chemical Reviews · doi:10.1021/acs.chemrev.8b00564 · Cited by 599
Pickering Interfacial Catalysis for Biphasic Systems: From Emulsion Design to Green Reactions
Pera‐Titus, M., Leclercq, L., Clacens, J., De Campo, F., & Nardello‐Rataj, V. (2015) · Angewandte Chemie International Edition · doi:10.1002/anie.201402069 · Cited by 493
Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition
Ramamurthy, V., & Sivaguru, J. (2016) · Chemical Reviews · doi:10.1021/acs.chemrev.6b00040 · Cited by 459
Molecular reactions at aqueous interfaces
Ruiz-Lopez, M. F., Francisco, J. S., Martins-Costa, M. T. C., & Anglada, J. M. (2020) · Nature Reviews Chemistry · doi:10.1038/s41570-020-0203-2 · Cited by 411
More Sustainable Approaches for the Synthesis of N-Based Heterocycles
Candeias, N. R., Branco, L. C., Gois, P. M. P., Afonso, C. A. M., & Trindade, A. F. (2009) · Chemical Reviews · doi:10.1021/cr800462w · Cited by 403
Liang, Y., Liu, S., Xia, Y., Li, Y., & Yu, Z. (2008) · Chemistry – A European Journal · doi:10.1002/chem.200701725 · Cited by 369
Acceleration of reaction in charged microdroplets
Lee, J. K., Banerjee, S., Nam, H. G., & Zare, R. N. (2015) · Quarterly Reviews of Biophysics · doi:10.1017/s0033583515000086 · Cited by 317
Solvent‐Free and Catalysts‐Free Chemistry: A Benign Pathway to Sustainability
Gawande, M. B., Bonifácio, V. D. B., Luque, R., Branco, P. S., & Varma, R. S. (2014) · ChemSusChem · doi:10.1002/cssc.201300485 · Cited by 317
Mortenson, D. E., Brighty, G. J., Plate, L., Bare, G., Chen, W., Li, S., Wang, H., Cravatt, B. F., Forli, S., Powers, E. T., et al. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.7b08366 · Cited by 292
Oriented Electric Fields Accelerate Diels–Alder Reactions and Control the endo/exo Selectivity
Meir, R., Chen, H., Lai, W., & Shaik, S. (2010) · ChemPhysChem · doi:10.1002/cphc.200900848 · Cited by 288
Chen, W., Dong, J., Plate, L., Mortenson, D. E., Brighty, G. J., Li, S., Liu, Y., Galmozzi, A., Lee, P. S., Hulce, J. J., et al. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b02960 · Cited by 286
Recent efforts directed to the development of more sustainable asymmetric organocatalysis
Hernández, J. G., & Juaristi, E. (2012) · Chemical Communications · doi:10.1039/c2cc30951c · Cited by 254
Spontaneous formation of gold nanostructures in aqueous microdroplets
Lee, J. K., Samanta, D., Nam, H. G., & Zare, R. N. (2018) · Nature Communications · doi:10.1038/s41467-018-04023-z · Cited by 253
Metadata
- Authors
- Jung, Y., & Marcus, R. A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-03-28
- Volume
- 129
- Issue
- 17
- Pages
- 5492-5502
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2170185477
- Cited by
- 702
- References
- 0
- FWCI
- 19.31
- Type
- journal article
- Language
- en
- Open access
- closed
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
Data sources
Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.
