个人简介

2015 American Chemical Society James Flack Norris Award in Physical Organic Chemistry 2014 Murray Goodman Endowed Chair 2013 Andrew Streitwieser Lecturer, UCBerkeley 2012 Wawzonek Memorial Lecturer, University of Iowa 2011 Visiting Professor, Gothenburg Univrsity 2008 Phi Beta Kappa lecturer, UCSD 2001 UCSD Chancellor's Associates' Faculty Excellence Award for teaching 1994 UCSD Academic Senate Distinguished Teaching Award 1993 Danish Research Academy Visiting Professor 1986 NATO Visiting Professor, University of Padua 1984 Fellow, Amer. Assn. Adv. Science 1972-1973 NIH Special Research Fellow, Gothenburg University 1967 Alfred P. Sloan Fellow 1963 NSF Postdoctoral Fellow, University of California, Berkeley

研究领域

Organic Chemistry

Our research in physical-organic chemistry is concerned with molecular structure, mechanisms of organic reactions, and effects of structure on reactivity. Areas of current activity include NMR studies of hydrogen-bond symmetry, of isotope effects, of stereochemical effects on reactivity, of the anomeric effect, and of steric hindrance. Is a hydrogen bond symmetric or asymmetric? The NMR method of isotopic perturbation can answer this for monoanions of 18O-labeled dicarboxylic acids and for various NHN species. The former had always been considered as having a symmetric intramolecular hydrogen bond. Nevertheless, the observed 13C spectra show that all of these exist as a pair of tautomers in solution. Cationic groups were thought to prefer the equatorial position on a sugar molecule. We reinvestigated this so-called reverse anomeric effect by measuring axial/equatorial ratios of various glucosylamines and glycosylimidazoles. The conformational changes that occur upon N-protonation can be accounted for on the basis of steric effects and an enhancement of the normal anomeric effect. Substituted glucosylanilines fine-tune the localization of positive charge, which increases the steric hindrance to ionic solvation but enhances the anomeric effect to an even greater extent. A highly accurate (±0.002 pH units!) NMR titration method, applicable to a mixture of closely related molecules, has been developed. We use this method to measure isotope effects on basicity and steric hindrance to ionic solvation. For amines we have demonstrated that the increased basicity on deuteration is of stereoelectronic origin. In contrast, computations and experimental evidence show that the well-known reduction of one-bond NMR coupling constants is not due to lone-pair delocalization, even though this had been the accepted interpretation for forty years. We have discovered a remarkable new reaction, the addition of nucleophiles to a p-benzyne biradical. As evidence, we showed that the enediyne cyclodeca-1,5-diyn-3-ene, in the presence of lithium halide and a weak acid, can be converted to a good yield of 1-halotetrahydronaphthalene. The reaction is simply first-order in enediyne, and independent of the concentrations of acid and halide. These kinetics are consistent with rate-limiting cyclization to a p-benzyne biradical that rapidly adds halide, to form an aryl anion, which is then protonated. The reaction thus involves nucleophilic addition of halide, which is novel and quite different from the usual radical reactivity of a p-benzyne biradical.

近期论文

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Charles L. Perrin "Half a century of research, teaching, service", J. Phys. Org. Chem., 2014, Perrin, C. L., Burke, K. D. "Variable-Temperature Study of Hydrogen-Bond Symmetry in Cyclohexene-1,2-dicarboxylate Monoanion in Chloroform-d", J. Am. Chem. Soc., 2014, Vol. 136, 4355-4362 Perrin, C. L., Reyes-Rodriguez, G. J. "Selectivity and Isotope Effects in Hydronation of a Naked Aryl Anion", J. Am. Chem. Soc., 2014, Vol. 136, 15263-15269 Charles L. Perrin "Relation between Errors in Enthalpy and Entropy", J. Phys. Org. Chem., 2013, Vol. 26, 269-270 Perrin, C. L., Reyes-Rodriguez, G. J. "Reactivity of Nucleophiles toward a p-Benzyne Derived from an Enediyne", J. Phys. Org. Chem., 2013, Vol. 26, 206-210 Perrin CL, Flach A, Manalo MN, "Decomposition of malonic anhydrides.", J Am Chem Soc, 2012, Vol. 134, Issue 23, 9698-707 [View Abstract] Perrin CL, Karri P, Moore C, Rheingold AL, "Hydrogen-bond symmetry in difluoromaleate monoanion.", J Am Chem Soc, 2012, Vol. 134, Issue 18, 7766-72 [View Abstract] Perrin, C. L.; Zhao, C. "Intramolecular Kinetic Isotope Effect in Hydride Transfer from Dihydroacridine to a Quinolinium Ion. Rejection of a Proposed Two-Step Mechanism with a Kinetically Significant Intermediate", Org. Biomol. Chem., (2008), 6, 3349-3353. Perrin, C. L.; Dong, Y. "Secondary Deuterium Isotope Effects on Acidity of Carboxylic Acids and Phenols", J. Am. Chem. Soc. (2007), 129, 4490-4497. Perrin, C. L.; Rodgers, B. L.; O'Connor, J. M. "Nucleophilic Addition to a p-Benzyne Derived from an Enediyne: A New Mechanism for Halide Incorporation into Biomolecules" J. Am. Chem. Soc. (2007), 129, 4795-4799. Perrin, C. L.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdélyi, M. "Stereochemistry of beta-Deuterium Isotope Effects on Amine Basicity", J. Am. Chem. Soc. (2005), 127, 9641-9647. Perrin, C. L., "Is There Stereoelectronic Control in Formation and Cleavage of Tetrahedral Intermediates?", Acc. Chem. Res. (2002), 35, 28-34. Perrin, C. L. "Are Short, Low-Barrier Hydrogen Bonds Unusually Strong?" Acc. Chem. Res., 2010, 43, 1550. Perrin, C. L.; Flach, A. "No Contribution of an Inductive Effect to Secondary Deuterium Isotope Effects on Acidity" Angew. Chem. 2011, 50,7674. Perrin, C. L.; Karri, P. "Position-Specific Secondary Deuterium Isotope Effects on Basicity of Pyridine" J. Am. Chem. Soc., 2010, 132, 12145. Perrin, C. L.; Lau, J. S.; Kim, Y.-J.; Karri, P.; Moore, C.; Rheingold,A. L. "Asymmetry of the 'Strongest' OHO Hydrogen-Bond, in the Monoanion of (±)-a,a'-Di-tert-butylsuccinate", J. Am. Chem. Soc., 2009, 131, 13548; 2010, 132, 2099