Xavier Creary

Xavier Creary

Mechanistic Studies in Organic Chemistry

Biography

1994-2017
Charles L. Huisking Professor of Chemistry, University of Notre Dame
1986-1994
Professor, University of Notre Dame
1980-1986
Associate Professor, University of Notre Dame
1974-1980
Assistant Professor, University of Notre Dame
1973-1974
Postdoctoral Research Associate, University of California, Santa Cruz
1973
Ph.D. in Chemistry, The Ohio State University
1968
B.S. in Chemistry, Seton Hall University

Selected Awards

2016, 2011
Joyce Award for Excellence in Undergraduate Teaching
2007
College of Science Shilts-Leonard Teaching Award
2006, 2002, 1999
Kaneb Teaching Award
1993
Thomas P. Madden Teaching Award
1977-1979
Alfred P. Sloan Fellowship

Research Interests

Professor Creary's research interests are a blend of synthetic and mechanistic organic chemistry. Studies in his laboratory are directed toward the study of novel reaction mechanisms and reactive intermediates. Reactions that proceed via carbocations, carbenes, free radicals, radical anions and radical cations are current areas of interest.

In the carbocation area, studies are directed toward so-called "electron deficient cations", [R2CE]+. Studies have shown that a variety of such carbocations that are substituted with electron-withdrawing groups E (such as carbonyl, phosphoryl, and sulfonyl) can be generated and, in certain instances, are more stable than expected on the basis of the electron-withdrawing properties of the group E.

Substitution mechanisms of halodiazirines are also of interest. It has been found via 15N labeling studies, that under appropriate conditions, either C-azidodiazirines, or N-azidodiazirines, can be formed as transient intermediates when halodiazirines react with azide ion. Substitution reactions can proceed via Sn2' or SRN1 mechanisms. The possible involvement of the isomeric and formally antiaromatic diazirinyl anions is under investigation.

Carbene chemistry, and the effect of neighboring silicon on carbenic centers, is also an area of current interest. We have generated a number of silicon containing carbenes, and these carbenes rearrange to give products that are indicative of a special interaction between silicon and the carbenic center. Silicon-activated hydrogen migration to carbenic centers is one of the facile processes that silyl carbenes undergo.

A novel β-thiolactam forming reaction has been discovered in our laboratory starting with readily available aryl esters. Subsequent ozonolysis allows preparation of a variety of b-lactam systems. The mechanism, scope, and obvious synthetic utility of this reaction are currently under investigation, as are carbocationic intermediates derived from such systems.

Recent Papers

  • Creary, X.; Chormanski, K.; Peirats, G.; Renneburg, C. "Electronic Properties of Triazoles. Experimental and Computational Determination of Carbocation and Radical-Stabilizing Properties." J. Org. Chem. 2017, 82(11), 5720-5730.
  • Creary, X. "3-Trimethylsilylcycloalkylidenes, gamma-Silyl vs. gamma-Hydrogen Migration to Carbene." J. Org. Chem. 2015, 80(22), 11378-11387.
  • Creary, X.; Heffron, A.; Going, G.; Prado, M. "gamma-Trimethylsilylcyclobutyl Carbocation Stabilization." J. Org. Chem. 2015, 80(3), 1781-1788.
  • Creary, X.; Heffron, A. "gamma-Silyl-Substituted Norbornyl Carbocations and Carbenes." J. Org. Chem. 2014, 79 (6), 2547-2555.
  • Creary, X. "3-Trimethylsilylcyclobutylidene. The gamma-Effect of Silicon on Carbenes." J. Am. Chem. Soc. 2013, 135 (17), 6570-6578.
  • Creary, X.; Anderson, A.; Brophy, C.; Crowell, F.; Funk, Z. "Method for Assigning Structure of 1,2,3-Triazoles." J. Org. Chem. 2012, 77 (19), 8756-8761.

Contact Information

  • Professor Emeritus
  • Office: 369/368 Stepan
  • Phone: 574-631-5861
  • Send an email