The central focus of the Singleton research group is the study of organic, organometallic, and bioorganic reaction mechanisms, and the key tool that we use in these studies is the determination o kinetic isotope effects (KIEs). In the mid-1990's, we developed a method for the high precision combinatorial determination of small KIEs at natural abundance by NMR. Its direct applicability to complex unlabeled reactants makes this methodology 1-2 orders of magnitude faster than studies requiring labeling. At the same time, it is much more versatile - our technique can look at a great number of reactions that would have been impractical or impossible to study by labeling or mass spectral methods, and the choice of reactants can be readily changed in response to each new experimental result. The simultaneous determination of a complete set of 13C, 2H, and 17O isotope effects possible with our methodology provides a much greater level of information than available from conventional methods. In addition, substantial evidence has accumulated supporting the reliable accuracy of our results.
- Roytman, V. A., & Singleton, D. A. (2020). Solvation Dynamics and the Nature of Reaction Barriers and Ion-Pair Intermediates in Carbocation Reactions. Journal of the American Chemical Society. 142(29), 12865-12877.
- Leibfarth, F., Helms, B. A., Pentzer, E., Singleton, D. A., & Lutkenhaus, J. (2020). When Is an Article ‘Good’ Enough?. Trends in Chemistry. 2(4), 278-279.
- Roytman, V. A., Jin, S., Nguyen, V. T., Nguyen, V. D., Haug, G. C., Larionov, O. V., & Singleton, D. A. (2019). Bond Memory in Dynamically Determined Stereoselectivity. Journal of the American Chemical Society. 142(1), 85-88.
- Roytman, V. A., & Singleton, D. A. (2019). Comment on “Activation of methane to CH3+: A selective industrial route to methanesulfonic acid”. SCIENCE. 364(6440), eaax7083-eaax7083.
- Kurouchi, H., & Singleton, D. A. (2018). Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity. Nature Chemistry. 10(2), 237-241.
- Biswas, B., Collins, S. C., & Singleton, D. A. (2014). Insights into the facility of "forbidden" [1,2]-sigmatropic rearrangements. ACS National Meeting Book of Abstracts. 248,
- Scully, A., Andujar-De Sanctis, I. L., & Singleton, D. A. (2014). Diels-Alder reactions between cyclopentadiene and trans-B-nitrostyrene derivatives: Exploring the free energy landscapes. ACS National Meeting Book of Abstracts. 247,
- Biswas, B. B., Collins, S., & Singleton, D. A. (2013). Origin of common competition between "allowed" [2,3]- and "forbidden" [1,2]- sigmatropic rearrangements: A mechanistic investigation. ACS National Meeting Book of Abstracts. 246,
- Singleton, D. A., & Waas, J. R. (2012). Reaction of tropone with dienes: [6+4] vs. [8+2] cycloaddition. ACS National Meeting Book of Abstracts. 244,
- Singleton, D. A. (2008). ORGN 295-Failure of the transition state paradigm in common organic reactions. ACS National Meeting Book of Abstracts. 236,
- New Concepts In Organic Selectivity and Mechanisms awarded by National Institutes of Health 2011 - 2016
- Association of Former Students University-Level Distinguished Achievement Award, The conferred by Texas A&M University - (College Station, Texas, United States) - University-Level Teaching 2008
- Biswas, Bibaswan (2015-08). Mechanistic Investigation of Rearrangement of Ammonium Ylides. (Doctoral Dissertation)
- Andujar-De Sanctis, Ivonne (2014-12). Unusual Intramolecular Kinetic Isotope Effects: Selectivity beyond Transition State Theory's Jurisdiction. (Doctoral Dissertation)
- Chen, Zhuo (2013-12). Isotope Effects, Dynamic Effects and Mechanisms of [2+2] Cycloadditions. (Doctoral Dissertation)
- Plata, Robert Erik (2013-08). Experimental Observations in the Morita Baylis-Hillman Reaction in Methanol. (Doctoral Dissertation)
- Quijano, Larisa Mae Mangaliman 1984- (2012-12). Observation and Nature of Non-statistical Dynamic Effects in Ordinary Organic Reactions. (Doctoral Dissertation)