John Chisholm  Assistant Professor Organic chemistry, catalysis, total synthesis, organometallic chemistry jdchisho@syr.edu phone: 315-443-6894 / fax: 315-443-4070 Office: CST 4-006 Education: • B.S., 1992, Alma College • Ph.D., 2000, University of California, Irvine • Postdoctoral Fellow, 2000-2002, Stanford University Honors & Awards: • Bristol-Myers Squibb Graduate Fellowship, 1999-2000 • National Institute of Health Postdoctoral Fellowship, 2000-2002 Courses: • CHE 275: Organic Chemistry • CHE 326*: Organic Chemistry Laboratory • CHE 427/627: Intermediate Organic Chemistry • CHE 575: Organic Spectroscopy   * denotes current Spring '08 course

Research Interests The long-term objective of my group is to develop new methods for organic synthesis and apply these methods in the synthesis of complex molecules. Catalytic techniques are of special interest because catalysts for organic reactions are not limited to simple rate acceleration, but can be modified to control the relative and absolute stereochemistry of the reaction products. The development of new catalysts for organic reactions is therefore a major goal. Some current research areas are shown below: Rhodium Catalyzed Alkyne Addition Reactions We have found that alkynes will react with aldehydes, 1,2-diketones and 1,2-ketoesters in the presence of a rhodium catalyst. These reactions occur under mild conditions which are tolerant of functional groups (alcohols, ketones, carboxylic acids, etc.) that have to be protected under standard conditions. Addition to enolizable 1,2-diketones and 1,2-ketoesters is also notable, as these substrates are problematic because they enolize readily (protecting them from attack) and often self-condense. Rhodium catalysis is also effective in the 1,4-addition of alkynes to α,β-unsaturated ketones. This reaction shows similar functional group tolerance as the addition to 1,2-diketones. New methods for the conjugate addition of alkynes are important because organocopper chemistry (the standard method of 1,4-addition for carbon nucleophiles) fails with alkynes. Palladium-Catalyzed Alkyne Addition Reactions Palladium catalysis has been found to be effective for the addition of alkynes to strained rings, such as cyclopropenes. This reaction has been found to proceed in excellent yield in the presence of aldehydes, alcohols and carboxylic acids. The alkynylcyclopropane products provide ready access to vinylcyclopropanes, which are valuable synthetic intermediates. Complex Molecule Total Synthesis We are also interested in developing new synthetic routes to complex molecules with interesting biological activity. Maoecrystal V and apicularen A both show significant cytotoxicity in in vitro assays, which may have application in the treatment of cancer. Fondosin B is an interleukin-8 inhibitor, which could potentially be used to treat autoimmune disorders. Peyssonenyne A and B are DNA methyltransferase inhibitors, which could potentially reverse tumor growth. Grandisine A binds to a specific opiod receptor, which may provide pain relief with fewer side effects. New synthetic routes to these compounds are currently being explored. Selected Publications Dhondi, P. K.; Carberry, P.; Choi, L. B.; Chisholm, J. D. "Addition of Alkynes to Aldehydes and Activated Ketones Catalyzed by Rhodium-Phosphine Complexes." J. Org. Chem. 2007, 72, 9590-9596. Dhondi, P. K.; Carberry, P.; Chisholm, J. D. "Ligand Effects in the Rhodium-Catalyzed Addition of Alkynes to Aldehydes and Diketones. Modification of the β-Diketonate Ligand." Tetrahedron Lett. 2007, 48, 8743-8746. Ganci, G. R.; Chisholm, J. D. "Rhodium-Catalyzed Addition of Aryl Boronic Acids to 1,2-Diketones and 1,2-Ketoesters." Tetrahedron Lett. 2007, 48, 8266-8269. Yin, J.; Gallis, C. E.; Chisholm, J. D. "Tandem Oxidation/Halogenation of Aryl Allylic Alcohols Under Moffatt-Swern Conditions." J. Org. Chem. 2007, 72, 7054-7057. Yin, J.; Chisholm, J. D. "Palladium-Catalyzed Addition of Alkynes to Cyclopropenes." Chem. Commun. 2006, 6, 632-634. » View all Publications