Gary A. Molander
Hirschmann-Makineni Professor of Chemistry
Office: 4001 IAST
Phone: (215) 573-8604
Fax: (215) 573-7165
Research Group Website: http://molandergroup.chem.upenn.edu/
Research StatementThe central theme of the Molander group's research is the development of new synthetic methods and their application to the synthesis of organic molecules. The group's focus is to expand and improve the Suzuki coupling reaction for organoboron compounds. Robust, air- and water-stable potassium organotrifluoroborates (R-BF3K), are employed to carry out couplings under relatively mild conditions using non-toxic components.
Greener Routes to Standard Reagents
The preparation of aryl- and heteroaryl potassium trifluoroborate and trihydroxyborate salts has been modified to take advantage of atom-economical boron sources, such as bis-boronic acid (BBA) and tetrakis(dimethylamino)diboron, which allow low catalyst loading and relatively mild reaction conditions. Reactive boronic acid species are generated, and subsequent coupling reactions with these substrates allow greener access to biaryl products.
Improving Transformations with More Robust Reagents
Organotrifluoroborates allow installation of functional groups within a molecule in the place of an existing carbon-boron bond. This allows one to prepare or purchase a simple, functionalized organotrifluoroborate and to elaborate the structure, drawing on the reactivity of the boron species. Some of the transformations carried out to date in this way are outlined below, highlighting the ability to install a cyclopropyl, hydroxymethyl, or nitroso functional group using potassium trifluoroborates.
Novel Reagents and Transformations
Some methods have been developed for the synthesis of novel reagents containing alkyltrifluoroborates, namely potassium aminomethyl-, hydroxymethyl-, and a-alkoxyalkyltrifluoroborates. The synthesis of these structures is outlined below with their applications in cross coupling illustrated.
Education and Academic History
- Ph. D., Purdue University (1979)
- B.S., Iowa State University (1975)
- National Institutes of Health Postdoctoral Fellowship, University of Wisconsin, Madison (1980-81)
- Alfred P. Sloan Research Fellowship (1987-1991)
- American Cyanamid Academic Awardee (1989)
- Chemical Society Arthur C. Cope Scholar Award (1998)
- Japanese Society for the Promotion of Science Fellowship (2002)
- American Chemical Society, Philadelphia Section Award (2003)
- Christian R. and Mary F. Lindback Award for Distinguished Teaching, University of Pennsylvania (2006)
Selected PublicationsG. A. Molander, L. Cavalcanti, “Oxidation of Organotrifluoroborates via Oxone”, J. Org. Chem., 76, 623-630 (2011)
J. Raushel, D. L. Sandrock, K. V. Josyula, D. Pakyz, G. A. Molander, “A Reinvestigation of Aminomethyltrifluoroborates and their Application in Suzuki–Miyaura Cross-Coupling Reactions”, J. Org. Chem., 76, 2762-2769 (2011)
G. A. Molander, N. Fleury-Brégeot, M. A. Hiebel, “Synthesis and Cross-Coupling of Sulfonamidomethyltrifluoroborates”, Org. Lett., 13, 1694-1697 (2011)
G. A. Molander, V. Colombel, V. A. Braz, “Direct Alkylation of Heteroaryls Using Potassium Alkyl- and Alkoxymethyltrifluoroborates”, Org. Lett., 13, 1852-1855 (2011)
G. A. Molander, I. Shin, “Synthesis and Suzuki-Miyaura Cross-Coupling Reactions of Potassium Boc-Protected Aminomethyltrifluoroborate with Aryl and Hetaryl Halides”, Org. Lett. 13, 3956-3959 (2011)
G. A. Molander, F. Beaumard, “Cross-Coupling of Mesylated Phenol Derivatives with Potassium Alkoxymethyltrifluoroborates”, Org. Lett. 13, 3948-3951 (2011)
G. A. Molander, L. Cavalcanti, “Metal-free Chlorodeboronation of Organotrifluoroborates”, J. Org. Chem. 76, 7195-7203 (2011)
G. A. Molander, F. Beaumard, T. K. Niethamer, “Cross-Coupling of Mesylated Phenol Derivatives with Potassium Cyclopropyltrifluoroborate”, J. Org. Chem. 76, 8126-8130 (2011)
G. A. Molander, S. A. McKee, “Copper-Catalyzed β-Boration of α,β−Unsaturated Carbonyl Compounds with Tetrahydroxydiborane”, Org. Lett. 13, 4684-4687 (2011)
G. A. Molander, F. Beaumard, “Cross-Coupling of Mesylated Phenol Derivatives with Potassium Ammonio- and Amidomethyltrifluoroborates”, Org. Lett. 13, 1242-1245 (2011)