Keith A. WoerpelProfessor |
|
|
Research Interests |
Organic and Organometallic Chemistry | |
| URL | www.chem.uci.edu/~kwoerpel | |
|
Academic Distinctions |
AstraZeneca Excellence in Chemistry Award Camille Dreyfus Teacher-Scholar Award Glaxo Wellcome Chemistry Scholar Award Cottrell Scholar Award from the Research Corporation Presidential Early Career Award for Scientists and Engineers from the White House Office of Science and Technology Policy UCI Academic Senate Distinguished Assistant Professor for Research Award UCI Academic Senate Distinguished Assistant Professor for Teaching Award |
|
| Appointments |
NIH Postdoctoral Fellow, University of California at Berkeley Joined UCI faculty in 1994 |
|
|
Research Abstract |
Our research is directed toward the development of new methods for organic synthesis, with the specific goal to develop unknown or poorly documented reactions into stereoselective carbon-carbon bond-forming processes. The reactions that particularly interest us are those that proceed by unique reaction mechanisms to afford products with control of stereochemistry. Silacyclopropanes as Intermediates for Organic Synthesis. Our studies of silacyclopropane chemistry revealed that these strained-ring compounds can be powerful tools for stereoselective organic synthesis. We have recently observed the first diastereoselective silacyclopropanations of chiral, functionalized alkenes (eq 1), and that these reactions can be employed to construct highly substituted cyclohexanes such as 3. We have also optimized a metal-catalyzed silacyclopropanation of alkenes that allows for the preparation of a wide range of silacyclopropanes under mild conditions. We are currently devising nantioselective variants of these reactions as well as developing new transformations of these silanes.  [3 + 2] Annulation Reactions of Allylic Silanes. We have been interested in employing allylic silanes to construct highly substituted five-membered ring heterocycles with high stereoselectivity (for example, eq 2). In addition to studies aimed at developing new annulation transformations, we have applied these reactions to the synthesis of the several natural products, including peduncularine, blastmycinone, and citreoviral.   Stereoselective Reactions of Oxocarbenium Ions. We have observed that reactions proceeding via oxocarbenium ion intermediates can exhibit selectivities that are counterintuitive. For example, the sense of stereoselectivity observed upon nucleophilic substitution on six-membered ring acetals depends upon the electronic nature of the substituents (eq 3). Our studies of these transformations have provided stereoelectronic models to understand and predict outcomes such as those shown in eq 3. We are discovering new and related phenomena, developing new models, and using these ideas to devise strategies for the syntheses of natural products such as vincarodine and laurefucin.   |
|
| Publications | "Stereospecific and Regioselective Reactions of Silacyclopropanes with Carbonyl Compounds Catalyzed by Copper Salts: Evidence for a Transmetalation Mechanism," Franz, A. K.; Woerpel, K. A. J. Am. Chem. Soc. 1999, 121, 949-957. | |
| "Low Temperature Silacyclopropanation of Mono- and Disubstituted Alkenes." Cirakovic J, Driver TG, Woerpel KA J. Am. Chem. Soc. 2002, in press. | ||
| "Diastereoselective Silacyclopropanations of Functionalized Chiral Alkenes." Driver TG, Franz AK, Woerpel KA, J. Am. Chem. Soc. 2002, 124, 6524. | ||
| "Synthesis of ()-epi-Citreoviral and ()-Citreoviral and the Kinetic Resolution of an Allylic Silane by a [3 + 2] Annulation." Peng Z-H, Woerpel KA, Org. Lett. 2002, in press. | ||
| "Stereochemical Reversal of Nucleophilic Substitution Reactions Depending Upon Substituent: Reactions of Heteroatom-Substituted Six-Membered Ring Oxocarbenium Ions Through Pseudo-Axial Conformers," Romero, J. A. C.; Tabacco, S. A.; Woerpel, K. A. J. Am. Chem. Soc. 2000, 122, 168-169. | ||
| Link to this profile | http://www.faculty.uci.edu/profile.cfm?faculty_id=2193 | |
| Last updated | 04/12/2007 | |
