ORGN 578 |
| Bin Chen, Department of Chemistry, University of Michigan, 930 North University, Ann Arbor, MI 48109 and Anna K. Mapp, Department of Medicinal Chemistry and Department of Chemistry, University of Michigan, 930 N University, Ann Arbor, MI 48109-1055. |
| [3,3]-Sigmatropic rearrangements have long been a mainstay of synthetic organic chemistry due to the relative ease with which carbon-carbon bonds can be assembled with excellent regio- and stereocontrol to produce structurally complex targets. In contrast, there are few such rearrangements available for selective carbon-nitrogen bond formation despite the enormous potential of such methods for the synthesis of molecules containing nitrogen-bearing stereocenters. We describe here the first example of a phosphorimidate to phosphoramidate [3,3]-rearrangement for the controlled formation of carbon-nitrogen bonds, including quaternary centers. This novel transformation is readily carried out in one pot starting from readily available allylic alcohols and thus provides rapid access to single stereoisomers of allylic amines, essential building blocks of structurally complex targets such as α- and β-amino acids, lactams, and alkaloid natural products. |
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New Reactions, Methodology, Heterocycles, Aromatics
8:00 PM-10:00 PM, Wednesday, August 25, 2004 Pennsylvania Convention Center -- Hall D, Poster
Division of Organic Chemistry |