John Wiseman

Dr. Wiseman's research group is engaged in synthesis of compounds possessing significant pharmacological activity. They are also interested in the synthesis of strained organic compounds, especially bridgehead alkenes, and exploration of their chemistry. Bridgehead alkenes are bridged bicyclic compounds having carbon-carbon double bonds with one terminus at a bridgehead position. The bridgehead double bond is twisted and distorted and the strain imparts high reactivity toward even mild reagents. The group prepared several members of this class in order to assess the relationships of strain, structure and reactivity. In some cases, the bridgehead alkenes are so reactive that they have only a fleeting lifetime and evidence of their existence is based only on the products of their reactions.

Dr. Wiseman's group has been employing an approach involving Diels-Alder reactions between quinones and ortho-xylylenes (ortho-quinodimethanes). This work has led to efficient syntheses of anti-cancer drugs, daunomycin and demethoxydaunomycin. The ortho-xylylenes are reactive intermediates which must be generated in the presence of reagents with which they are to react (i.e., the quinones). In parallel with the synthetic work, there is exploration of the methods of generating the ortho-xylylenes to better understand the mechanisms of the reactions.

Representative Publications

J.R. Wiseman, N.I. Frcnch and R.K. Hallmark, "The ortho-Quinodimethane Route to Anthracyclinones. A New Synthesis of 4-Demethoxydaunomvcinone," Tetrahedron Lett. (1978), 3765.

W.K. Chwang, A.J. Kresge and J.R. Wiseman, "Hydrolysis of Strained Bridgehead Bicyclic Vinyl Ethers and Sulfides," J. Am. Chem. Soc. (1979), 101, 6972.

J.R. Wiseman and J.E. Kipp, Bicyclo[3.3.1]non-1-ene," J. Am. Chem. Soc. (1982),104, 4688.

J.R. Wiseman and S.Y. Lee, "Synthesis of Anatoxin-a," J. Org. Chem. (1986), 51, 2485.

M. Strumpel, C.B. Quinn, J.R. Wiseman and C.E. Nordman "Crystallographic Characterization of Reaction Intermediates with Bridgehcad Double Bonds: Structures of Diels-Alder Adducts of (E) and (Z)-9-Thiabicyclo[3.3.1] non-l-ene Derivatives with 1,3 Diph enylisobenzofuran," Acta Crystallogr, Part 2 (1990), B46, 229.

Research Areas(s)

• Organic Chemistry
  Synthetic Organic Chemistry
  Mechanisms of Chemical Reactions