Organic Transformations

The major focus of our work is the design and development of processes leading to the formation of new organic compounds. Microwave assisted synthesis has had a dramatic effect on how synthetic chemists approach the preparation of new compounds. Rapid reaction rates, ultralow catalyst loadings, and the minimization of secondary reactions are only some of the benefits of microwave assisted chemistry. The blending of microwave assisted chemistry with carbon heteroatom bond forming reactions facilitates the generation of new and intriguing compounds. One aspect of our research program is focused on the synthesis of new organic compounds through the design and development of new microwave assisted transformations.

Some of our recent developments (undergraduates underlined):
  • Microwave Assisted Regioselective Addition of P(O)-H Bonds to Alkenes Without Added Solvent or Catalyst. R. I. Taylor, L.E. Thompson, P.B. Patel. and R.A. Stockland Jr. Org. Lett. 2005, 7, 851.

  • Organosoluble Copper Clusters as Precatalysts for Carbon-Heteroelement Bond Forming Reactions: Microwave and Conventional Heating. G. F. Manbeck, A. J. Lipman, R. A. Stockland Jr., A. L. Freidl, A. F. Hasler, J. J. Stone, and I. A. Guzei J. Org. Chem. 2005, 70, 244.

  • Remarkable tolerance of ethynyl steroids to air and water in hydrophosphinylation reactions: Reaction scope and limitations. R. A. Stockland Jr. A. J. Lipman, J. A. Bawiec, P. E. Morrison, I. A. Guzei, P. M. Findeis, J. F. Tamblin. J. Organomet. Chem. 2006, 691, 4042.

  • Development of a Room Temperature Hirao Reaction,  Kohler, M.C.; Sokol, J. G.; Stockland, R. A., Jr. Tetrahedron Lett. 2009, 50, 457.

  • Probing the Steric Limits of Rhodium Catalyzed Hydrophosphinylation.  P-H addition vs. Dimerization/Oligomerization/Polymerization, M.E. Richard, K. P Reese, J. J. Stone, P. D. Pickett, E. S. Tillman, R. A. Stockland Jr., J. Organomet. Chem. 2011, 696, 123-129.  Invited contribution for a special issue on catalytic addition of E-H bonds to non-activated carbon-carbon multiple bonds       

  • Phospha-Michael Additions to Activated Internal Alkenes: Steric and Electronic Effects. Lenker, H, K.; Richard, M. E.; Reese, K. P.; Carter, A. F.; Zawisky, J. D.; Winter, E. F.; Bergeron, T. W.; Guydon, K. S.; Stockland, R. A., Jr. J. Org. Chem. 2012, 77, 1378-1385.

  • Acid, silver, and solvent-free gold catalyzed hydrophenoxylation of internal alkynes.  M. E. Richard, D. V. Fraccica, K. J. Garcia, E. J. Miller, R. M. Ciccarelli, E. C. Holahan, V. L. Resh, A. Shah, P. M. Findeis, and R. A. Stockland Jr.  Beilstein J. Org. Chem. 2013, 9, 2002-2009  Invited contribution to a thematic series on gold catalysis edited by Dean Toste.  Our paper was one of the top 5 most downloaded original research articles for October/November 2013.
Mechanistic Investigations
Understanding the discrete steps of chemical reactions is a critical area of research. Through the synthesis, characterization and study of model transition metal complexes, we hope to provide insight into the importance and relevance of key transformations. Our initial studies have involved the synthesis and investigation of metal phosphonate complexes as reactive intermediates in metal mediated P-C bond forming reactions. Work is currently underway to develop novel methodology and new catalysts based upon this mechanistic work.

Some of our recent developments (undergraduates underlined):
  • Reductive Elimination from Metal Phosphonate Complexes: Circumvention of Competing Protonolysis Reactions. R. A. Stockland Jr., A. M. Levine, M. T. Giovine; I. A. Guzei, and J. C. Cannistra Organometallics 2004, 23, 647.

  • Steric and Electronic Effects on Arylphosphonate Elimination from Organopalladium Complexes. M. C. Kohler, R. A. Stockland Jr., and N. P. Rath Organometallics 2006, 25, 5746.

  • Arylpalladium Phosphonate Complexes as Reactive Intermediates in Phosphorus-Carbon Bond Forming Reactions M. C. Kohler, T. V. Grimes, X. Wang, T. R. Cundari, R. A. Stockland Jr. Organometallics 2009, 28, 1193.

  • P-H activation using alkynylgold substrates: steric and electronic effects. G.F. Manbeck, M.C. Kohler, M.R. Porter, and R.A. Stockland Jr. Dalton Transactions 2011 40, 12595-12606.

  • Rapid Synthesis of Arylgold Compounds Using Dielectric Heating. H.K. Lenker, T.G. Gray and R.A. Stockland Jr. Dalton Trans.2012, 41, 13274-13276

Bioorganometallic Chemistry

Organometallic complexes were once thought to be of little importance to biological chemistry, however, compounds containing well defined metal-carbon bonds have recently been used as anticancer agents, radiopharmaceuticals, and bioprobes. Our interest in this area is focused on the design of new complexes where the metal center is providing a unique geometry or reactive site for biological residues. Additionally, the synthesis of new model systems for biological processes is of interest.

Some of our recent developments (undergraduates underlined):
  • Organometallic Complexes Containing 17-Ethynyl-17 beta -hydroxyandrost-4-en-3-one and Related Ethynyl Steroids. R. A. Stockland Jr., M. C. Kohler, I. A. Guzei, Margaret E. Kastner, and J. A. Bawiec, III, R. B. Hochberg, D. C. Labaree Organometallics, 2006, 25, 2475.

  • Resolved P-Metallated Nucleoside Phosphoramidites. E. J. Miller, K. J. Garcia, E. C. Holahan, R. M. Ciccarelli, R. A. Bergin, S. L. Casino, T. L. Bogaczyk, M. R. Krout, P. M. Findeis, and R. A. Stockland Jr. Inorg. Chem. (accepted, in press). 

Books and Book chapters

Practical Functional Group Synthesis.  Robert A. Stockland, Jr., Wiley, 2015


Microwave Heating as a Tool for Clean Organic Synthesis.  Robert A. Stockland, Jr. in Microwave Heating as a Tool for Sustainable Chemistry. Leadbeater, N. E. ed. CRC Press, 2010


Modern NMR Spectroscopy in Education, ACS symposium Series Volume 969, Eds. David S. Rovnyak and Robert A. Stockland, Jr., 2007