The first project tackled by the group at Kansas involved the development of oxaziridines as intermediates for ring-expansion chemistry. Specifically, we learned that symmetrical, cyclic ketones could be transformed to chiral lactams by the group-selective process shown below. Such a group-selective transformation could be applied to problems in asymmetric induction as shown as well as utilized in more standard types of regiochemical control. This technology was subsequently applied to total synthesis problems, including the total syntheses of (-)-yohimbine and carnitine in enantiomerically pure form.
Lead References
Reference 4 below is a review article that summarizes our efforts in this area.
1. Selectivity in an Asymmetric Nitrogen Insertion Reaction. Aubé, J.; Burgett, P. M.; Wang, Y. Tetrahedron Lett. 1988, 29, 151-154. This isn't really such an important paper, but it was the first work that we published from KU so it is included here for sentimental value.
2. Synthetic Aspects of an Asymmetric Nitrogen Insertion Process: Preparation of Chiral, Non-Racemic Caprolactams and Valerolactams. Total Synthesis of (–)-Alloyohimbane. Aubé, J.; Wang, Y.; Hammond, M.; Tanol, M.; Takusagawa, F.; Vander Velde, D. J. Am. Chem. Soc. 1990, 112, 4879-4891.
3. Symmetry-Driven Synthesis of Indole Alkaloids: Asymmetric Total Syntheses of (+)-Yohimbine, (–)-Yohimbone, (–)-Yohimbane, and (+)-Alloyohimbane. Aubé, J.; Ghosh, S.; Tanol, M. J. Am. Chem. Soc. 1994, 116, 9009-9018.
4. Oxaziridine Rearrangements in Asymmetric Synthesis. Aubé, J. Chem. Soc. Rev. 1997, 26, 269-277.
5. On the Stereochemistry of the Oxidation of Imines Derived from Substituted Cyclohexanones: Axial vs. Equatorial Attack and Evidence for Delivery by an Adjacent Hydroxyl Group. Wang, Y.; Chackalamannil, S.; Aubé, J. J. Org. Chem. 2000, 65, 5120-5126.
For More Information Contact:
Department of Medicinal Chemistry
4070 Malott Hall
Tel: 785-864-4495
FAX: 785-864-5326
Internet: jaube@ku.edu
