List of Faculty
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Inorganic Chemistry; Organometallic Chemistry; Synthetic Organic Methods; Activation of Aromatic Molecules.
The central theme of our research program concerns the activation of aromatic molecules as synthons for polycyclic natural products. The cornerstone of this approach is to selectively and reversibly dearomatize arenes and aromatic heterocycles through η²-complexation to a transition metal. Coordination serves to enhance the reactivity of the aromatic ligand, to stabilize reactive intermediates, thereby facilitating assembly of various alicyclic and polycyclic structures, to direct the stereochemistry of these chemical transformations, and to protect the site of coordination for future transformations.
Once developed, this technology could have a dramatic impact on the ability
of synthetic chemists to rapidly and efficiently produce small quantities
of biologically active compounds or derivatives of these materials, which
in turn would facilitate the execution of structure/activity relationship
studies required for optimization of new pharmaceuticals.
Consider for example, the compound below, which is the product of benzene
undergoing a Diels-Alder reaction promoted by rhenium(I) at 20°C:
Current research in the group falls into five main areas: 1) elementary
transformations of η²-arene complexes, 2) elementary transformations
of η²-heterocycle complexes, 3) multi-step convergent synthesis
of natural products, 4) design and synthesis of chiral aromaphiles,
and 5) development of low-valent Re, Mo, and W coordination chemistry.
Selected Publications:
Dihapto-Coordinated Amide, Ester, and Aldehyde Complexes and Their Role in Decarbonylation. Graham, P. M., Mocella, C. J., Sabat, M., Harman, W. D. Organometallics. 2005. 24: 911-919.
A New Generation of π-Basic Dearomatization Agents. Keane, J. M., Harman, W. D. Organometallics. 2005. 24: 1786-1798.
Tungsten(0) η²-Thiophene Complexes: Dearomatization of Thiophene and Its Facile Oxidation, Protonation, and Hydrogenation. Delafuente, D. A., Myers, W. H., Sabat, M., Harman, W. D. Organometallics. 2005. 24: 1876-1885.
Diastereo- and Enantioselective Dearomatization of Rhenium-Bound Naphthalenes. Ding, F., Valahovic, M. T., Keane, J. M., Anstey, M. R., Sabat, M., Trindle, C. O., Harman, W. D. J. Org. Chem. 2004. 69(7): 2257-2267.
Solid-State Induced Control of Kinetically Unstable Stereoisomers. Keane, J. M., Ding, F., Sabat, M., Harman, W. D. J. Am. Chem. Soc. 2004. 126: 785.
Stereoselective Tandem 1,4-Addition Reactions for Benzenes: A Comparison of Os(II), Re(I), and W(0) Systems. Ding, F. and Harman, W. D. J. Am. Chem. Soc. 2004. 126(42): 13752-13756.
Michael Addition Reactions with Dihapto-Coordinated Anisoles: Controlling the Stereochemistry of the Para and Benzylic Carbons. Smith, P. L., Keane, J. M., Shankman, S. E., Chordia, M., Harman W. D. J. Am. Chem. Soc. 2004. 126(47): 15543-15551.
The Dearomatization of Arenes By Dihapto-Coordination. Harman, W. D. in Topics in Organometallic Chemistry, vol 7, Transition Metal Arene π Complexes in Organic Synthesis and Catalysis, Kundig, E. P. Ed., Springer: Berlin 2004.
Conformational and Linkage Isomerizations for Dihapto-coordinated Arenes and Aromatic Heterocycles: Controlling the Stereochemistry of Ligand Transformations. Harman, W. D. Coord. Chem. Rev. 2004. 248: 853-866.
Coordination Chemistry and Properties of Unusually π-Basic Molybdenum Fragments. Mocella, C. J., Delafuente, D. A., Keane, J. M., Warner, G. R., Friedman, L. A., Sabat, M., Harman, W. D. Organomet. 2004. 23: 3772-3779.
Transition Metal-Stabilized Arenium Cations: Protonation of Arenes Dihapto-Coordinated to π-Basic Metal Fragments. Keane, J. M., Chordia, M. D., Mocella, C. J., Sabat, M., Trindle, C. O., Harman, W. D. J. Am. Chem. Soc. 2004. 126: 6806-6815.
Rhenium Promoted Diastereo- and Enantioselective Cyclopentannulation Reactions: Furans as 1,3-Propene Dipoles. Friedman, L. A., You, F., Sabat, M., Harman, W. D. J. Am. Chem. Soc. 2003. 125: 14980.
Computational Modeling of Complexes of Pentaammineosmium(II) with Aromatic Ligands. Trindle, C., Sacks, G., Harman, W. D. Int. J. Qunat. Chem. 2003. 92: 457.
In Vitro Metabolism of Tolcapone to Reactive Intermediates: Relevance to Tolcapone Liver Toxicity. Smith, K. S., Smith, P. L., Heady, T. N., Trugman, J. M., Harman, W. D., Macdonald, T. L. Chem. Res. Toxicol. 2003. 16: 123.
Computational Study of Methane Activation by TpRe(CO)2 and CpRe(CO)2 with a Stereoelectronic Comparison of Cyclopentadienyl and Scorpionate Ligands. Bergman, R. G., Cundari, T. R., Gillespie, A. M., Gunnoe, T. B., Harman, W. D., Klinckman, T. R., Temple, M. D., White, D. P. Organometallics. 2003. 22 (11): 2331.
Stereoselective Aldehyde Addition to Rhenium-Coordinated Furans. Schiffler, M. A., Friedman, L. A., Brooks, B. C., Sabat, M., Harman, W. D. Organometallics. 2003. 22: 4966.
Formation of o-Quinone Methides from Dihapto-Coordinated Phenols and Their Controlled Release from a Transition Metal to Generate Chromans. Stokes, S. M., Ding, F., Smith, P. L., Keane, J. M., Kopach, M. E., Jervis, R., Sabat, M., Harman, W. D. Organometallics. 2003. 22: 4170.
Dearomatization of Benzene, Deamidization of N,N-Dimethylformamide, and a Versatile New Tungsten π Base. Graham, P. M., Meiere, S. H., Sabat, M., Harman, W. D. Organometallics. 2003. 22: 4364.
Binding and Activation of Aromatic Molecules by a Molybdenum π-Base. S.H. Meiere, J.M. Keane, T.B. Gunnoe, M. Sabat, W.D. Harman. J. Am. Chem. Soc. 2003. 125 (8): 2024.
Pentaammine(triflato)osmium(III)triflate. Electronic Encyclopedia of Reagents for Organic Synthesis, 2002.
TpRe(L)(Br)2 (Tp = hydridotris(pyrazolyl)borate); L = tBuNC, PMe3, pyridine (py), 1-methylimidazole (MeIm). Electronic Encyclopedia of Reagents for Organic Synthesis, 2002.
Evaluation of Muscarinic Agonist-Induced Analgesia in Muscarinic Acetylcholine Receptor Knockout Mice. Duttaroy, A., Gomeza, J., Gan, J., Basile, A. S., Harman, W. D., Smith, P. L., Felder,C. C., Levey, A. I., Wess, J. Mol. Pharmacol. 2002. 62: 1084.
Dihapto Coordination of Carboxylic Acid Derivatives with an Asymmetric Rhenium π-Base: A New Mechanism for Amide Isomerization? S.H. Meiere, F. Ding, L.A. Friedman, M. Sabat, W.D. Harman. J. Am. Chem. Soc. 2002. 124: 13506.
A Strategy for the Resolution of a Chiral Dearomatization Agent: {TpRe(CO)(1-methylimidazole)} Coordination of α-Pinene (Tp = hydridotris(pyrazolyl)borate). S.H. Meiere, M.T. Valahovic, and W.D. Harman. J. Am. Chem. Soc. 2002. 124: 15099.
Ligand-Modulated Stereo- and Regioselective Tandem Addition Reactions of Rhenium-Bound Naphthalene. M.T. Valahovic, T.B. Gunnoe, M. Sabat, W.D. Harman. J. Am. Chem. Soc. 2002. 124: 3309.
Tandem 1,4-Addition Reactions with Benzene and Alkylated Benzenes Promoted by Pentaamineosmium(II). F. Ding, M.E. Kopach, M. Sabat, W.D. Harman. J. Am. Chem. Soc. 2002. 124: 13080.
Cycloaddition Reactions of Dihapto-Coordinated Furans. L.A. Friedman, M.S. Sabat, W.D. Harman. J. Am. Chem. Soc. 2002. 124: 7395.
Discrimination of Enantiofaces and Stereoselective Electrophilic Addition Reactions for η²- Pyrrole Complexes. M.T. Valahovic, W.H. Myers, W.D. Harman. Organometallics. 2002. 21: 4581.
Methanol Addition to Dihapto Coordinated Rhenium Complexes of Furan. L.A. Friedman, W.D. Harman. J. Am. Chem. Soc. 2001. 123: 8967.
Organometallic Complexes of Osmium, Gonzalez, J. Harman, W. D. in Science of Synthesis, Vol. 1, Organometallics, Lautens, M. Ed. Thieme: New York 2001.
Binding Selectivity of Dihapto-Coordinated Olefins, Ketones, and Aldehydes Utilizing the Asymmetric ?-Basic Metal Fragment {TpRe(CO)(1-methylimidazole)} (Tp = hydridotris(pyrazolyl)borate) Meiere, S. H.; Harman, W. D. Organometallics 2001, 20, 3876.
Coordination of Aromatic Molecules by the Asymmetric p-Bases {TpRe(CO)(L)} Meiere, S. H.; Brooks, B. C. Gunnoe, T. B.; Carrig, E. H.; Sabat, M. Harman, W. D. Organometallics 2001, 20, 3661.
Synthetic Applications of the Dearomatization Agent Pentaammineosmium(II). P.L. Smith, M.D. Chordia, W.D. Harman. Tetrahedron. 2001. 8203.
A Facile Diels-Alder Reaction with Benzene: Synthesis of the Bicyclo[2.2.2]octene Skeleton Promoted by Rhenium. M.D. Chordia, P.L. Smith, S.H. Meiere, M. Sabat, W.D. Harman. J. Am. Chem. Soc. 2001. 123: 10756.
Ethene Rotation in Chiral Octahedral Rhenium(I) Complexes. Friedman, L. A., Brooks, B. C., Meiere S. H., Harman, W. D. Inorg Chem. 2001. 20: 1699.
A Promising New Dearomatization Agent: Crystal Structure, Synthesis, and Reactions of the Versatile Complex TpRe(CO)(1-methylimidazole)(η²-benzene). S.H. Meiere, B.C. Brooks, T.B. Gunnoe, M. Sabat, and W.D. Harman. Organometallics. 2001. 20: 1038-1040.
The Inter- and Intrafacial Linkage Isomerizations of Rhenium Complexes with Aromatic Molecules. B.C. Brooks, S.H. Meiere, L.A. Friedman, T.B. Gunnoe, E. Carrig, W.D. Harman. J. Am. Chem. Soc. 2001. 123: 3541-3550.
Dearomatization of Naphthalene: Novel Stereoselective Cyclization Reactions Promoted by Osmium(II). M.D. Winemiller and W.D. Harman. J. Org. Chem. 2000. 65: 1249-1256.
Asymmetric Dearomatization of η²-Arene Complexes: Synthesis of Stereodefined Functionalized Cyclohexenones and Cyclohexenes. M.D. Chordia, W.D. Harman. J. Am. Chem. Soc. 2000. 122: 2725.
Stereoselective Dihapto-Binding of Prochiral Aromatic Compounds by {TpRe(CO)(PMe3)}: Synthesis, Characterization, Stability, and Enantiofacial Discrimination (Tp = hydrido(tris)pyrazolylborate). T.B. Gunnoe, M. Sabat and W. D. Harman. Organometallics. 2000. 19: 728-740.
Development of Muscarinic Analgesics Derived from Epibatidine: Role of the M4 Receptor Subtype. J.L. Ellis, W.D. Harman, J. Gonzalez, M.L. Spera, R. Liu, T.Y. Shen, D.M. Wypij, F.J. Zuo. Pharmacol. Exp. Ther. 1999. 288: 1143.
Enantiofacial Discrimination in Dihapto-Coordination of Aromatic Molecules by the Chiral π-Base/σ-Lewis Acid TpRe(CO)(PMe3). T. B. Gunnoe, M. Sabat and W.D. Harman. J. Am. Chem. Soc. 1999. 121: 6499.
Activation of Styrenes Towards Diels-Alder Cycloadditions by Osmium(II): Synthesis of Stereodefined Decalin Ring Systems. S. Kolis, M.D. Chordia, R. Liu, M.E. Kopach, W.D. Harman. J. Am. Chem . Soc. 1998. 120: 2218.
Dearomatization of Furan: Elementary Transformations of η²-Coordinated Furan Complexes of Pentaammineosmium(II). H. Chen, R. Liu, W.H. Myers, W.D. Harman. J. Am. Chem. Soc. 1998. 120: 509.
Stereodefined Tandem Addition Reactions of η²-Arenes: A Versatile Route to Functionalized Cyclohexenes. M.E. Kopach, S.P. Kolis, R. Liu, J.W. Robertson, M.D. Chordia, W.D. Harman. J. Am. Chem. Soc. 1998. 120: 6199.
Activation of Benzylic Carbons of η²-Arene Complexes: Osmium Promoted Michael-Aldol Cyclization Reactions of 3-Alkylated Anisoles that Form Functionalized Decalins. S.P. Kolis, M.E. Kopach, R. Liu, W.D. Harman. J. Am. Chem. Soc. 1998. 120: 6205.
Asymmetric Induction in η²-Arene Complexes of Pentaammineosmium(II). M.D. Chordia, W.D. Harman. J. Am. Chem. Soc. 1998. 120: 5637.
Dearomatization of Naphthalene: Stereoselective cis-1,4 Tandem Additions Promoted by Osmium(II). M.D. Winemiller, W.D. Harman. J. Am. Chem. Soc. 1998. 120: 7835.
Reactions of TpRe(CO)2(THF) with Aromatic Molecules. T.B. Gunnoe, M. Sabat, W.D. Harman. J. Am. Chem. Soc. 1998. 120: 8747.
The Activation and Manipulation of Pyrroles by Pentaammineosmium(II). L.M. Hodges, W.D. Harman. Adv. in Nitrogen Heterocycles. Moody, C. J. ed.; JAI Press: Stamford. 1998. 3: 1-44.
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