The present work consists primarily of the four projects. The first is methodology for silyl triflate-mediated Dieckmann-like cyclization between esters and imides. The second project is the second generation synthesis of a natural product UCS1025A, which included optimization of the synthesis of the triene precursor of UCS1025A and exploration of its biomimetic Intra-Molecular Diels-Alder (IMDA) cycloaddition. A more efficient way to synthesize the corresponding triene via the MeMgBr-mediated addition of the corresponding vinyl iodide to the enal and optimization of the diastereoselectivity of the final Diels-Alder-cycloaddition to produce UCS1025A are described.
The third project, described in Chapter II, is synthetic efforts toward total synthesis of the related natural product CJ-16,264. We have studied the diastereoselective IMDA cycloaddition of the corresponding chiral aldehyde precursor in the presence of MacMillan catalyst followed by BEt3-promoted Reformatski-coupling with iodolactones in the synthesis of various diastereomeric analogs of CJ-16,264.
The final project, described in Chapter III, is the synthetic efforts total synthesis of the natural products phomopsichalasin and diaporthichalasin, which we envision to be biosynthesized via a series of two sequential and spontaneous IMDA cycloadditions. Several approaches to the heterocyclic portion of the natural products and their tetraene precursor are described.
University of Minnesota Ph.D. dissertation. June 2009. Major: Chemistry. Advisor: Thomas R. Hoye. 1 computer file (PDF); xi, 273 pages. Ill. (some col.)
Sizova, Elena P..
Second generation synthesis of UCS1025A. synthetic efforts toward total syntheses of CJ-16,264 and Phomopsichalasin..
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