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A Case Study of the Mechanism of Alcohol-Mediated Morita Baylis–Hillman Reactions. The Importance of Experimental Observations
Open accessAbstract
The mechanism of the Morita Baylis-Hillman reaction has been heavily studied in the literature, and a long series of computational studies have defined complete theoretical energy profiles in these reactions. We employ here a combination of mechanistic probes, including the observation of intermediates, the independent generation and partitioning of intermediates, thermodynamic and kinetic measurements on the main reaction and side reactions, isotopic incorporation from solvent, and kinetic isotope effects, to define the mechanism and an experimental mechanistic free-energy profile for a prototypical Morita Baylis-Hillman reaction in methanol. The results are then used to critically evaluate the ability of computations to predict the mechanism. The most notable prediction of the many computational studies, that of a proton-shuttle pathway, is refuted in favor of a simple but computationally intractable acid-base mechanism. Computational predictions vary vastly, and it is not clear that any significant accurate information that was not already apparent from experiment could have been garnered from computations. With care, entropy calculations are only a minor contributor to the larger computational error, while literature entropy-correction processes lead to absurd free-energy predictions. The computations aid in interpreting observations but fail utterly as a replacement for experiment.
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Metadata
- Authors
- Plata, R. E., & Singleton, D. A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-03-13
- Volume
- 137
- Issue
- 11
- Pages
- 3811-3826
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2324958041
- Cited by
- 445
- References
- 42
- FWCI
- 27.87
- Type
- journal article
- Language
- en
- Open access
- hybrid
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