Roger K. Murray, Ph.D.

Professor
Disciplines Taught: Chemical Biology, Chemistry
Office: Science Center 417
Phone: (610) 660-1789
Fax: (610) 660-1783
Email: rmurray@sju.edu


I received an A.B. in Chemistry from Cornell University in 1964. As a National Science Foundation Undergraduate Research Participant, I investigated the chemistry of small ring compounds with Dr. Donald G. Farnum. My education continued at Michigan State University where I received a Ph.D. in Chemistry in 1969. As a National Institutes of Health Predoctoral Fellow, I explored the photochemistry of some conjugated cyclic ketones with Dr. Harold Hart. From 1969-1971, I was a National Institutes of Health Postdoctoral Fellow with Dr. Kurt Mislow at Princeton University where I worked in organophosphorus chemistry. In 1971, I joined the faculty of the Department of Chemistry at the University of Delaware. I was named a Camille and Henry Dreyfus Teacher Scholar for 1976-1981, and I spent the 1977-1978 academic year as a Fulbright-Hays Visiting Professor at the Universite de Reims in France. From 1984-1988, I served as the Assistant Chair and Director of Graduate Studies in the Department of Chemistry at the University of Delaware. In 1997, I moved to Saint Joseph's University as Professor and Chair of the Department of Chemistry. I have published fifty-nine papers on aspects of organic photochemistry and the synthesis and chemistry of cage compounds related to adamantane and its derivatives. 

Education

  • A.B. Cornell University (1964)
  • Ph.D. Michigan State University (1969) 

Courses Taught

I teach the sections of Organic Chemistry I and II that are for students who are not majoring in chemistry.

Organic Chemistry I (CHM 2311) provides an introduction to the fundamental aspects of structure and bonding in organic compounds by the study of alkanes, alkenes, alkynes, and aromatic compounds. The major classes of organic compounds that contain functional groups: alcohols and ethers, aldehydes and ketones, carboxylic acids and their derivatives, and amines are covered in Organic Chemistry II (CHM 2321). A knowledge of the properties and chemical reactivities of these compounds facilities our discussion of the structures of carbohydrates and proteins. 

Publications

Selected Publications

H. Hart and R. K. Murray, Jr., "Electrophilic Oxidation of 1,2,3,4-Tetramethylnaphthalene and the Photochemistry of Benzo-2,4-cyclohexadienones", J. Org. Chem., 32, 2448 (1967).

H. Hart, R. H. Schlosberg, and R. K. Murray, Jr., "The Acetylation of Phenylcyclopropane", J. Org. Chem., 33, 3800 (1968).

R. K. Murray, Jr. and H. Hart, "Contrast Between Thermal and Photochemical Reverse Diels-Alder Reactions Involving Ketones", Tetrahedron Lett., 4995 (1968).

H. Hart and R. K. Murray, Jr., "The Photosensitized Rearrangement of Benzobicyclo[2.2.2]octadienones",Tetrahedron Lett., 379 (1969).

H. Hart and R. K. Murray, Jr., "An Unusual Substituent Effect in the Photorearrangement of Benzobicyclo[2.2.2]octadienols", J. Am. Chem. Soc., 91, 2183 (1969).

R. K. Murray, Jr. and H. Hart, "Reaction of Azodicarboxylates with 2,4-Cyclohexadienones: 1,4-Cycloaddition and 'Ene' Reactions", Tetrahedron Lett., 4781 (1969).

H. Hart, R. K. Murray, Jr., and G. D. Appleyard, "Direct and Sensitized Photoisomerizations of a Diazabicyclo[2.2.2]octenone", Tetrahedron Lett., 4785 (1969).

H. Hart and R. K. Murray, Jr., "On the Mechanism of the Photoisomerization of 1(2H)-Naphthalenones", J. Org. Chem., 35, 1535 (1970).

W. B. Farnham, R. A. Lewis, R. K. Murray, Jr., and K. Mislow, "Lithium Aluminum Hydride Induced Stereomutation of Secondary Phosphine Oxides", J. Am. Chem. Soc., 92, 5808 (1970).

W. B. Farnham, R. K. Murray, Jr., and K. Mislow, "Stereospecific Alkylation of Menthyl Phenylphosphinate", J. Am. Chem. Soc., 92, 5809 (1970).

W. B. Farnham, R. K. Murray, Jr., and K. Mislow, "Stereospecific Free-Radical Addition of Menthyl Phenylphosphinate to Cyclohexene: Evidence for Retention of Configuration at Phosphorus", J. Chem. Soc. Chem. Commun., 146 (1971).

W. B. Farnham, R. K. Murray, Jr., and K. Mislow, "The Absolute Configuration of Menthyl Methylphosphinate: A Reassignment and Its Stereochemical Consequences", J. Chem. Soc. Chem. Commun., 605 (1971).

J. Donohue, N. Mandel, W. B. Farnham, R. K. Murray, Jr., K. Mislow, and H. P. Benschop, "Retention Stereochemistry in a Grignard Displacement Reaction at Chiral Phosphorus. The Absolute Configuration of Menthyl S-Methyl Phenylphosphonothioate", J. Am. Chem. Soc., 93, 3792 (1971).

R. K. Murray, Jr. and K. A. Babiak, "Wolff-Kishner Reduction of 8,9-Dehydro-2-adamantanone", J. Org. Chem., 38, 2556 (1973).

R. K. Murray, Jr. and T. K. Morgan, Jr., "Synthesis of 2,5-Disubstituted Protoadamantanes. Silver Ion-Assisted Acetolysis of 2-exo-Bromo-5-protoadamantanone", Tetrahedron Lett., 3299 (1973).

R. K. Murray, Jr., T. K. Morgan, Jr., H. Hart, and V. J. Hull, "On the Photodecarbonylation of β,γ-Epoxy Ketones", J. Org. Chem., 38, 3805 (1973).

R. K. Murray, Jr. and D. L. Goff, "Photochemistry of β,γ-Epoxy Ketones: Photoisomerization of 2,2,4,4-Tetramethyl-7-oxabicyclo[4.1.0]heptan-3-one", J. Chem. Soc. Chem. Commun., 881 (1973).

R. K. Murray, Jr. and K. A. Babiak, "Methanolic Sodium Borohydride Reduction with Hydrochloric Acid Work-up of 8,9-Dehydro-2-adamantanone: A Correction", Tetrahedron Lett., 311 (1974).

R. K. Murray, Jr. and K. A. Babiak, "Synthesis of 8,9-Dehydro-2-adamantanone by the Oxa-di-π-methane Photorearrangement of 2-Protoadamantenone", Tetrahedron Lett., 319 (1974).

R. K. Murray, Jr., B. L. Jelus, and K. A. Babiak, "Common Electron Impact Fragmentations of 2-Methoxy-8,9-dehydroadamantane and 2-exo-Methoxyprotoadamantene", Org. Mass Spectrom., 9, 710 (1974).

G. A. Olah, G. Liang, K. A. Babiak, and R. K. Murray, Jr., "Stable Carbocations. CLXXV. 8,9-Dehydro-2-adamantyl Cations", J. Am. Chem. Soc., 96, 6794 (1974).

B. L. Jelus, B. Munson, K. A. Babiak, and R. K. Murray, Jr., "Studies in Mass Spectrometry: A Comparison of the Electron Impact and Chemical Ionization Fragmentations of 8,9-Dehydro-2-adamantanol and 2-exo-Protoadamantenol", J. Org. Chem., 39, 3250 (1974).

R. K. Murray, Jr., T. K. Morgan, Jr., J. A. S. Polley, C. A. Andruskiewicz, Jr., and D. L. Goff, "The Photochemistry of β,γ-Epoxy Cyclic Ketones", J. Am. Chem. Soc., 97, 938 (1975).

R. K. Murray, Jr., D. L. Goff, and R. E. Ratych, "Synthesis of 9,10-Dehydrohomoadamantane", Tetrahedron Lett., 763 (1975).

R. K. Murray, Jr., T. K. Morgan, Jr., and K. A. Babiak, "Synthesis of 2-Substituted 8,9-Dehydroadamantanes",J. Org. Chem., 40, 1079 (1975).

B. L. Jelus, R. K. Murray, Jr., and B. Munson, "Studies in Chemical Ionization Mass Spectrometry: Secondary Alcohols with Isobutane", J. Am. Chem. Soc., 97, 2362 (1975).

R. K. Murray, Jr., K. A. Babiak, and T. K. Morgan, Jr., "Synthesis and Chemistry of 2,4-Dehydro-5-homoadamantanone", J. Org. Chem., 40, 2463 (1975).

R. K. Murray, Jr. and T. K. Morgan, Jr., "Synthesis of the 2,5-Protoadamantanediols", J. Org. Chem., 40, 2642 (1975).

G. A. Olah, G. Liang, K. A. Babiak, T. K. Morgan, Jr., and R. K. Murray, Jr., "Stable Carbocations. CLXXXIV. 2,4-Dehydro-5-homoadamantyl Cations", J. Am. Chem. Soc., 98, 576 (1976).

M. K. Jain, N. Y.-M. Wu, T. K. Morgan, Jr., M. S. Briggs, and R. K. Murray, Jr., "Phase Transition in a Lipid Bilayer. Influence of Adamantane Derivatives", Chem. Phys Lipids, 17, 71 (1976).

J. S. Polley and R. K. Murray, Jr., "Synthesis of 1,3-Bishomoadamantane", J. Org. Chem., 41, 3294 (1976).

R. K. Murray, Jr. and T. M. Ford, "Pyrolysis of the Lithium Salts of the p-Toluenesulfonylhydrazones of 8,9-Dehydro-2-adamantanone and 2,4-Dehydro-5-homoadamantanone", J. Org. Chem., 42, 1806 (1977).

R. K. Murray, Jr., J. S. Polley, S. S. Abdel-Meguid, and V. W. Day, "Synthesis and X-Ray Crystal Structure of 1,3,3,4,5,6-Hexamethyl-7-thiabicyclo[2.2.1]-hept-5-en-2-one 7-anti-Oxide", J. Org. Chem., 42, 2127 (1977).

< ;p>R. W. Colman, J. Kuchibhotla, M. K. Jain, and R. K. Murray, Jr., "Phase Separation in Phosphatidylcholine Bilayers as a Predictor of Inhibition of Blood Platelet Aggregation by Amantadines", Biochim. Biophys. Acta,467, 273 (1977).

 

R. K. Murray, Jr., D. L. Goff, and T. M. Ford, "Synthesis and Chemistry of 2,5-Dehydro-4-protoadamantanone", J. Org. Chem., 42, 3870 (1977).

R. K. Murray, Jr. and C. A. Andruskiewicz, Jr., "On the Photochemistry of 1-Oxaspiro[2.n]alkan-5-ones", J. Org. Chem., 42, 3994 (1977).

G. A. Olah, G. Liang, K. A. Babiak, T. M. Ford, D. L. Goff, T. K. Morgan, Jr., and R. K. Murray, Jr., "On the Structure of Cyclopropylcarbinyl and Cyclobutyl Cations: 8,9-Dehydro-2-adamantyl and 2,5-Dehydro-4-protoadamantyl Cations", J. Am. Chem. Soc., 100, 1494 (1978).

D. L. Goff and R. K. Murray, Jr., "Synthesis of 2-Substituted 4-Oxahomoadamantanes", J. Org. Chem., 43, 3179 (1978).

R. K. Murray, Jr. and D. L. Goff, "Synthesis of 1-Substituted Tricyclo-[3.3.1.02,7]nonanes", J. Org. Chem., 43, 3844 (1978).

R. K. Murray, Jr. and T. M. Ford, "Synthesis and Chemistry of 2,11-Dehydro-5-homoadamantanone", J. Org. Chem., 44, 3504 (1979).

R. K. Murray, Jr., T. M. Ford, G. K. S. Prakash, and G. A. Olah, "On the Structure of Cyclopropylcarbinyl and Cyclobutyl Cations. The 2,8-Dimethyl-8,9-Dehydro-2-adamantyl and 4-Phenyl-2,5-dehydro-4-protoadamantyl Cations", J. Am. Chem. Soc., 102, 1865 (1980).

B. Munson, B. L. Jelus, F. Hatch, T. K. Morgan, Jr., and R. K. Murray, Jr., "Stereochemical Effects in the Mass Spectra of 2-Hydroxy-, 5-Hydroxy-, and 2,5-Dihydroxyprotoadamantanes", Org. Mass Spectrom., 15, 161 (1980).

R. K. Murray, Jr. and T. M. Ford, "The Photochemistry of α'-Substituted β,γ-Cyclopropyl Cyclic Ketones. The Influence of Geometric Constraints and Substituent Effects on Competitive Norrish Type I Photoreactions", J. Am. Chem. Soc., 102, 3194 (1980).

J. M. Harris, J. R. Moffatt, M. G. Case, F. W. Clarke, J. S. Polley, T. K. Morgan, Jr., T. M. Ford, and R. K. Murray, Jr., "Reactivity of Geometrically Constrained Cyclopropylcarbinyl and Homoallyl Substrates. Solvolysis of 2,4-Dehydro-5-homoadamantyl and 2-Homoadamant-4-enyl Derivatives", J. Org. Chem., 47, 2740 (1982).

C. A. Andruskiewicz, Jr. and R. K. Murray, Jr., "The Fate of 2-Homoadamantyl Carbene", J. Org. Chem., 48, 1926 (1983).

R. J. Israel and R. K. Murray, Jr., "Competitive and Regiospecific Bridgehead Substitution in Electrophilic Oxidation Reactions of Homoadamantane", J. Org. Chem., 48, 4701 (1983).

J. J. Sosnowski and R. K. Murray, Jr., "Competitive Bridgehead Substitution in Electrophilic Oxidation Reactions of Ethanoadamantane", J. Org. Chem., 49, 2174 (1984).

J. J. Sosnowski and R. K. Murray, Jr., "Bridgehead Functionalization of [2]Diadamantane. Aspects of the Chemistry of 2- and 4-Monosubstituted [2]Diadamantanes", J. Org. Chem., 49, 4471 (1984).

R. J. Israel and R. K. Murray, Jr., "Copper(I)-Induced Reactions of the Adducts Formed from Cyclopropyl Ketones and [Tris(methylthio)methyl]lithium", J. Org. Chem., 50, 1573 (1985).

J. J. Sosnowski, E. B. Danaher, and R. K. Murray, Jr., "Competitive Bridgehead Substitution in Electrophilic Oxidation Reactions of Protoadamantane. Synthesis of 3-Protoadamantanol. On the Utility of Molecular Mechanics Calculations for Predicting the Bridgehead Reactivity of Hydrocarbons with Electrophiles", J. Org. Chem., 50, 2759 (1985).

J. J. Sosnowski, A. L. Rheingold, and R. K. Murray, Jr., "Bridgehead Functionalization of [1]Diadamantane",J. Org. Chem., 50, 3788 (1985).

R. J. Israel and R. K. Murray, Jr., "Synthesis of 4,5,9,10-Tetradehydroadamantan-2-one", J. Org. Chem., 50, 4703 (1985).

B. Munson, T.-M. Feng, H. D. Ward, and R. K. Murray, Jr., "Isobutane Chemical Ionization Mass Spectra of Unsaturated Alcohols", Org. Mass Spectrom., 22, 606 (1987).

H. D. Ward and R. K. Murray, Jr., "Synthesis of 1,1-Bishomoadamant-3-ene (Tricyclo[5.3.1.13,9]dodec-3-ene)", J. Org. Chem., 55, 81 (1990).

H. D. Ward, D. S. Teager, and R. K. Murray, Jr., "Ring Expansions of Simple Cyclic Conjugated Cyclopropyl Ketones by the Nozaki Method Are Not Regiospecific", J. Org. Chem., 57, 1926 (1992).

D. S. Teager, H. D. Ward, and R. K. Murray, Jr., "On the Reaction of (Dibromomethyl)lithium with Bicyclic and Tricyclic Ketones", J. Org. Chem., 58, 5493 (1993).

D. S. Teager and R. K. Murray, Jr., "Oxidation of 2,4-Didehydroadamantane", J. Org. Chem., 58, 5548 (1993).

D. S. Teager and R. K. Murray, Jr., "Synthesis of 5,5'-Bi-2-oxaadamantane", J. Org. Chem., 58, 5560 (1993).

G. A. Olah, H. A. Buchholz, G. K. S. Prakash, G. Rasul, J. J. Sosnowski, R. K. Murray, Jr., M. A. Kusnetsov, S. Liang, and A. de Meijere, "Triaxane-2-methyl Cation and 2,10-para-[32.56]Octahedranedimethyl Dication",Angew. Chem. Int. Ed. Engl., 35, 1499 (1996).

Research

My research program emphasizes the synthesis and chemistry of cage compounds related to adamantane and its derivatives. The conformational rigidity in the carbon frameworks of these compounds makes them useful as models for studies in physical organic chemistry. In addition, some simply substituted cage derivatives like amantadine and memantine show pronounced pharmacological activity.

Parkinson's disease is a condition of the central nervous system that afflicts at least one percent of the American population over the age of 50. Although the cause of this disease is unknown, it has been recognized for some time that the clinical symptoms of Parkinson's disease (e.g., alternating periods of uncontrollable violent shaking and rigidity) are due to a neurochemical defect in the dopamine producing neurons in the substantia nigra of the brain. An obvious treatment for Parkinson's disease would be to replace dopamine in the brain.

Unfortunately, dopamine itself does not cross the "blood-brain barrier". Consequently, a standard clinical treatment for the symptoms of Parkinson's disease is to provide the patient with oral doses of levodopa. This compound survives the gastrointestinal track, enters the blood stream, and successfully crosses the blood-brain barrier. Within the brain, an enzyme converts levodopa to dopamine. However, there are significant long-term problems that are associated with levodopa therapy.

In totally unrelated work, several years ago DuPont introduced amantadine (marketed under the name of Symmetrel) as the first orally active antiviral drug for the prevention of respiratory illness due to influenza viruses. By serendipity, it was established that treatment with amantadine improves the symptoms of some people who suffer from Parkinson's disease. This observation was totally unexpected since the structure of amantadine is unrelated to that of any other drug that is employed in the clinical treatment of this disease. Subsequent studies have shown that amantadine enters all cell membranes, crosses the blood-brain barrier, and has nearly ideal pharmacokinetic and metabolic profiles.

However, amantadine seems to have only a modest direct agonist action on postsynaptic dopaminergic receptors. If a derivative of amantadine could be developed that has a significant direct dopamine agonist component, then that compound would fulfill all of the criteria for an ideal drug for treating the symptoms of Parkinson's disease.

The structure-activity studies on amantadine that have been published have been restricted to the relatively simple modifications of changing the nature of the amine substituent and/or of introducing various alkyl groups onto the carbon skeleton of amantadine as in memantine. We are approaching this problem via the more synthetically challenging strategy of exploring how changes in the size and shape of the hydrocarbon cage of amantadine affect its antiparkinson activity. Preliminary studies have shown that increasing the size of the hydrocarbon cage in amantadine affords enhanced activity.
 


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