James Rigby

James Rigby

Research interest(s)/area of expertise

 Organic Chemistry

Research

Our research group is engaged in a wide variety of problems directed toward the total synthesis of pharmacologically active natural products. Several target molecules of current interest in the group are shown below. In addition to pursuing total synthesis the group is focused on developing novel synthetic methodology. For example, considerable effort has been committed to an investigation of chromium(0)-promoted higher-order cycloaddition reactions, which comprise a class of potentially very powerful transformations for constructing complex cyclic structures. Processes involving efficient [6π+4π] and [6π+2π] cycloadditions have been brought to practice recently in our laboratories, and targets such as the steroid, (+)-estradiol and the tropane alkaloid, (+)-ferruginine have been prepared using this technology. Most recently, a novel and very powerful chromium(0)-mediated multicomponent cycloaddition has been discovered in our laboratories which is proving to be an important addition to the synthetic armory. These multicomponent transformations are uniquely capable of producing rapid increases in molecular complexity, including the creation of considerable stereochemical information.

Our group is also actively engaged in studying novel reaction pathways that are characteristic of vinyl isocyanates. This intriguing functionality has proven to be a powerful and versatile building block for alkaloid synthesis. Numerous 4+2 and 4+1 cycloaddition processes have been discovered in this context and molecules such as the anticancer alkaloids, (+)-pancratistatin and (±)-tazettine have been synthesized with this chemistry. Recently, novel reactive intermediates known as nucleophilic carbenes have been found to be potent reaction partners in combination with isocyanates to deliver structurally and functionally elaborate advanced intermediates for alkaloid synthesis.

Education

• B.S., Case Western Reserve University, 1973
• Ph.D., University of Wisconsin-Madison, 1977
• Swiss NSF Postdoctoral Fellow, ETH-Zürich,1977-78
• NIH Post-Doctoral Fellow, Columbia University, 1978-9

Selected publications

• Rigby, J. H.; Wang, Z. “Synthesis of Highly Substituted Cyclopentenones via the [4 + 1] Cycloaddition of Nucleophilic Carbenes and Vinyl Ketenes”, Org. Lett. 2003, 5, 263–264
• Rigby, J. H.; Bazin, B.; Meyer, J. H.; Mohammadi, F. “Synthetic Studies on the Ingenane Diterpenes. An Improved Entry into a trans- Intrabridgehead System”, Org. Lett. 2002, 4, 799–801
• Rigby, J. H.; Kondratenko, M. A.; Fiedler, C. “Preparation of a Resin-Based Chromium Catalyst for Effecting [6 + 2] Cycloaddition Reactions”, Org. Lett. 2000, 2, 3917–3919
• Rigby, J. H.; Maharoof, U. S. M.; Mateo, M. E. “Studies on the Narciclasine Alkaloids: Total Synthesis of (+)-Narciclasine and (+)- Pancratistatin”, J. Am. Chem. Soc. 2000, 122, 6624–6628
• Rigby, J. H.; Laurent, S.; Dong, W.; Danca, M.D. “Bis(alkylthio)carbenes as Novel Reagents for Organic Synthesis”, Tetrahedron 2000, 56, 10101–10111