C-H Bond Functionalization
We are developing new catalysts and conditions to use various C-H groups
as precursors for C-X and C-C bond formation in complex settings
(Scheme 1). Particularly, we're interested in coordinatively directed
hydride abstraction, elaboration of azoles, and C-H
activation-initiated Heck-type reactions. To achieve these goals, we
will employ strategies of catalyst design, thus exploring novel
organometallic and coordination chemistry, and target-oriented new
organic reaction development.
Complex Molecule Synthesis
Simultaneously and synergistically with our new reaction campaigns, we are working to devise highly step economical
strategies for the preparation of potentially bioactive small
molecules. For example, we seek new tools to extend modern peptide
synthesis techniques to the preparation of azole oligomers and other
value-added building blocks that can be used as starting materials for
modular syntheses of natural products and other targets of medicinal,
biological, or materials interest (Scheme 2). We are currently pursuing
a concise approach to analogs of Kabiramide C and the tris(oxazole)
macrolide family of marine natural products based on this technology.
||Conley, B. L., Williams, T. J. "Dehydrogenation of ammonia-borane by Shvo's catalyst". Chem. Commun. 2010, 46, 4815-4817. |
||Conley, B. L., Williams, T. J. "Thermochemistry and Molecular Structure of a Remarkable Agostic Interaction in a Heterobifunctional Ruthenium-Boron Complex". J. Am. Chem. Soc. 2010, 132, 1764–1765. |
||Conley, B. L., Pennington-Boggio, M. K., Boz, E., Williams, T. J. "Discovery, Applications, and Catalytic Mechanisms of Shvo’s Catalyst". Chemical Reviews, 2009, 110, 2294-2312. |
||Driver, T. G.; Williams, T. J. Labinger, J. A.; Bercaw, J. E. "C-H Bond Activation by Dicationic Platinum(II) Complexes" Organometallics 2007, 26, 294-301.
T. J.; Labinger, J. A.; Bercaw, J. E. "Reactions of Indene and Indoles
with Platinum Methyl Cations: Indene C-H Activation, Indole pi versus
Nitrogen Lone-Pair Coordination" Organometallics 2007, 26, 281-287.
P. A.; Paxton, T. J.; Williams, T. J.; "Cyclopentadienone Synthesis by
Rhodium(I)-Catalyzed [3 + 2] Cycloaddition Reactions of Cyclopropenones
and Alkynes" J. Am. Chem. Soc. 2006, 128, 14814-14815.
P. A.; Haustedt, L. O.; Lim, J.; Love, J. A.; Williams, T. J.; Yoon,
J.-Y. "Asymmetric Catalysis of the [5 + 2] Cycloaddition Reaction of
Vinylcyclopropanes and pi-Systems" J. Am. Chem. Soc. 2006, 128, 6302-6303.
P. A.; Gamber, G. G.; Williams, T. J. "Rhodium(I)-Catalyzed [5+2],
[6+2], and [5+2+1] Cycloadditions: New Reactions for Organic Synthesis"
in Modern Rhodium-Catalyzed Transformations; Evans, P. A., Ed. Wiley:
New York, 2005.
||Wender, P. A.; Deschamps, N. M.; Williams, T. J. "Intermolecular Dienyl Pauson-Khand Reaction" Angew. Chem. Int. Ed. 2004, 43, 3076-3079.
||Wender, P. A.; Williams, T. J. "[(Arene)Rh(COD)]+ Complexes as Catalysts for [5+2] Cycloadditions" Angew. Chem. Int. Ed. 2002, 41, 4550-4553.