Studies Directed Toward the Synthesis of Enantioenriched Unsaturated Cyanohydrins and their Application in an Imidate [3,3] Sigmatropic Shift.
The overarching goal of this research is the development of synthetic methodologies that permit facile, enantiocontrolled access to molecules of biological importance. A one step reaction forms imidate (3) from its corresponding aldehyde (1) using HCN dissolved in ether, trichloroacetonitrile and DBU as a catalyst. This racemic reaction has allowed for the mass production of (3) to work out the conditions of the palladium reaction. (3) can also be derived from enantiomerically pure unsaturated cyanohydrins (2) upon treatment with trichloroacetonitrile and DBU. Upon exposure to a palladium(II) catalyst, 3 undergoes a stereospecific [3,3] rearrangement to form the related acetamide (4). To date, this reaction has been shown to form only trans double-bond products. These highly functionalized products offer great versatility as chiral building blocks for the preparation of enantioenriched pharmaceutical compounds.
Collier, Summer, "Studies Directed Toward the Synthesis of Enantioenriched Unsaturated Cyanohydrins and their Application in an Imidate [3,3] Sigmatropic Shift." (2000). URC Student Scholarship.
American Chemical Society-Petroleum Research Fund