Andrzej Sygula

Associate Professor of Organic Chemistry

	Andrzej Sygula is a native of Poland. He received his M.Sci. and Ph.D. degrees in chemistry from Jagiellonian University in 1976 and 1982 respectively. He was appointed as an assistant professor at his alma mater and held that position until 1991. Dr. Sygula has held research positions at Indianna Univerity-Purdue University, Louisiana State University, and Iowa State University. In 2003, he moved to the chemistry department at Mississippi State.
	email:
	telephone: (662) 325-7612

Research Interests

We have been involved in the synthesis and characterization of buckybowls (not buckyballs), i.e. novel polynuclear aromatic hydrocarbons (PAH) with curved surfaces with their carbon networks related to buckminsterfullerenes. The smallest member of the family is corannulene, C₂₀H₁₀ (1). Standard synthetic methodologies developed for planar PAH do not work well for buckybowls as a result of considerable strain involved. Originally we used the Flash Vacuum Pyrolysis (FVP) method to synthesize several buckybowls, including cyclopentacorannulene C₂₂H₁₀ (2) and two semibuckminsterfullerenes (C₃₀H₁₂) 3 and 4.

Most of our recent research activity has been directed toward development of more practical "wet-chemistry" methods for buckybowl syntheses. We have discovered that the critical ring formation step can be conveniently achieved by inexpensive procedures if sufficient strain is introduced into precursors. With this breakthrough we can now produce gram quantities of buckybowls, as well as larger systems not available by FVP due to volatility problems.

Beside the development of synthetic methodologies we have studied the properties of buckybowls. This includes conformational analysis, determination of the bowl-to-bowl inversion barriers as well as metal complexation studies of buckybowls with both alkali and transition metals by application of spectroscopic and computational methodologies.

Publications 2002 - 2007

Book Chapters

• "Synthesis and Chemistry of Polycyclic Aromatic Hydrocarbons with Curved Surfaces:Buckybowls" Sygula, A.; Rabideau, P. W. in "Carbon-Rich Compounds: From Molecules to Materials" Haley, M.; Tykwinski, R., Eds.; Willey-VCH Publisher, Weinheim, 2006, Chapter 12 , pp. 529 - 565.

Refereed Papers

66. "A Double Concave Hydrocarbon Buckycatcher" Sygula, A.; Fronczek, F. R.; Sygula, R.; Rabideau, P. W.; Olmstead. M. M. J. Am. Chem. Soc. 129, 3842 (2007).
65. "η⁶-Coordination of the Curved Carbon Surface of Corannulene (C₂₀H₁₀) to (η⁶-arene)M²⁺ (M = Ru, Os)" Zhu, B.; Ellern, A.; Sygula, A.; Sygula, R.; Angelici, R. J. Organometallics 26, 1721, (2007).
64. "Isocorannulenofuran: A Versatile Building Block for the Synthesis of Large Buckybowls" Sygula, A.; Sygula, R.; Rabideau, P. W. Org. Lett. 8, 5909-5911, (2006).
63. "The First Buckybowl Aryne: Corannulyne – a Nonplanar Benzyne" Sygula, A.; Sygula, R.; Rabideau, P. W. Org. Lett. 7, 4999, (2005).
62. "Flattening of a Curved-Surface Buckybowl (Corannulene) by η⁶-Coordination to {Cp*Ru}⁺" Vecchi, P. A.; Alvarez, C. M.; Ellern, A.; Angelici, R. J.; Sygula, A.; Sygula, R.; Rabideau, P. W. Organometallics, 24, 4543 (2005).
61. "Barrelene-Semibullvalene Rearrangement Indused by Visible Light: Synthesis of Dicorannulenosemibullvalene Dimethyl Dicarboxylate" Sygula, A.; Sygula, R. Rabideau, P. W. Tetrahedron Lett., 46, 1189 (2005).
60. "Synthesis and Structure of Dimetallated Buckybowl: Coordination of One [Cp*Ru]⁺ Unit to Each Side of Corannulene" Vecchi, P. A.; Alvarez, C. M.; Ellern, A.; Angelici, R. J.; Sygula, A.; Sygula, R.; Rabideau, P. W.; Angew. Chem. Int. Ed. Eng., 43, 4497 (2004).
59. "A novel twin corannulene: synthesis and crystal structure determination of dicorannuleobarrelene," A. Sygula, R. Sygula, A. Ellern and P.W. Rabideau Org. Lett. 5, 2595 (2003).
58. "Hexahapto corannulene buckybowl complexes of iridium, including ring-to-ring migration," C.M. Alverez, R.J. Angelici, A. Sygula, R. Sygula, and P.W. Rabideau Organometallics 22, 624 (2003).
57. "Improved Synthesis of Benz[a]acephenanthrene" Marcinow, Z.; Sygula, A.; Rabideau, P. W. Synlett. 2002, 183 9.
56. "Formation of the Corannulene Core by Nickel-Mediated Intramolecular Coupling of Benzyl and Benzylidene Bromides: A Versatile Synthesis of Dimethyl 1,2-Corannulene Dicarboxylate" Sygula, A.; Karlen, S. D.; Sygula, R.; Rabideau, P. W. Org. Lett. 2002, 4, 3135.
55. "The Addition of Organolithium Reagents to Corannulene and Conformational Preferences in 1-Alkyl-1,2-Dihydrocorannulenes" Sygula, A.; Sygula, R.; Fronczek, F. R.; Rabideau, P. W. J. Org. Chem. 2002, 67, 6487.

(Full publication list)