Gary A. Molander

Hirschmann-Makineni Professor of Chemistry
Organic Chemistry

Office: 4001 IAST
Phone: (215) 573-8604
Fax: (215) 573-7165
Email: gmolandrsasupennedu

Jump to: Research Statement | Education and Academic History | Selected Publications

Research Statement
The central theme of Professor Molander's research is the development of new synthetic methods and their application to the synthesis of organic molecules. Within this context, exciting and useful new ways to form carbon-carbon bonds selectively are being explored utilizing novel reagents as well as organometallic catalysts.
We have recently begun a program to expand and improve the Suzuki coupling reaction for organoboron compounds. The methods utilized employ air- and water-insensitive organotrifluoroborates (RBF3K), and the couplings occur under relatively mild conditions using non-toxic components. Some of the novel reagents that have been developed and their application in cross coupling are outlined below.

The organotrifluoroborates are robust species, allowing unprecedented transformations of functionality in the presence of the intact boron species. This allows one to prepare or purchase a simple, functionalized organotrifluoroborate, and to elaborate the structure around the boron species. As a result, this completely changes strategic planning for target-oriented synthesis, because one can now carry the valuable carbon-boron bond through multi-step synthetic sequence, cross-coupling at a point that is more efficient or convenient. Some of the transformations carried out to date in this way are outlined below.

Approaches to the total synthesis of several important natural products are being developed based on the methods outlined above. Included are asymmetric approaches to dehydrohomopumiliotoxins, zoapatanol, nakadomarin, halicyclamine A and apoptolidin.

Education and Academic History

Selected Publications
G. A. Molander, R. A. Oliveira, “Wittig Reaction of Formyl-Substituted Organotrifluoroborates and Stabilized Phosphonium Ylides in an Aqueous Medium”, Tetrahedron Lett. 49, 1266-1268 (2008).

Y. H. Park, H. R. Ahn, B. Canturk, S. I. Jeon, S. Lee, H. Kang, G. A. Molander, J. Ham, “A Facile One-Pot Preparation of Potassium Hydroxyaryl- and (Hydroxyalkyl)aryltrifluoroborates”, Org. Lett. 10, 1215-1218 (2008).

G. A. Molander, P. E. Gormisky, D. L. Sandrock, “Scope of Aminomethylations via Suzuki-Miyaura Cross-Coupling of Organotrifluoroborates”, J. Org. Chem. 73, 2052-2057 (2008).

G. A. Molander, D. E. Petrillo, “Suzuki-Miyaura Cross-Coupling of Potassium Trifluoroboratohomoenolates”, Org. Lett., 10, 1795-1798 (2008).

G. A. Molander, D. J. Cooper, “Functionalization of Organotrifluoroborates: Reductive Amination”, J. Org. Chem., 73, 3885-3891 (2008).

G. A. Molander, B. Canturk, “Preparation of Potassium Alkoxymethyltrifluoroborates and Their Cross-Coupling with Aryl Chlorides”, Org. Lett., ASAP.

G. A. Molander, W. Febo-Ayala, M. Ortega-Guerra, “Facile Synthesis of Highly Functionalized Ethyltrifluoroborates”, J. Org. Chem.,ASAP.

S. D. Dreher, P. G. Dormer, D. L. Sandrock, G. A. Molander, “Efficient Cross-Coupling of Secondary Alkyltrifluoroborates with Aryl Chlorides – Reaction Discovery Using Parallel Micro-Scale Experimentation”, J. Am. Chem. Soc. ASAP.