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. 142(29), 12865-12877.
- Leibfarth, F., Helms, B. A., Pentzer, E., Singleton, D. A., & Lutkenhaus, J. (2020). When Is an Article ‘Good’ Enough?. 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. 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.
- Kurouchi, H., & Singleton, D. A. (2018). Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity.. Nat Chem. (2), 241.
- Biswas, B., Collins, S. C., & Singleton, D. A. (2014). Insights into the facility of "forbidden" [1,2]-sigmatropic rearrangements. 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. 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. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY. 246,
- Singleton, D. A., & Waas, J. R (2012). Reaction of tropone with dienes: [6+4] vs. [8+2] cycloaddition. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY. 244,
- Singleton, D. A (2008). ORGN 295-Failure of the transition state paradigm in common organic reactions. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY. 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)