Synthesis of highly functionalized natural products from carbohydrates: Application of the [2,3] Wittig rearrangement and advancement toward nonlinear optical materials

Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)




James Kallmerten


Carbohydrates, Wittig rearrangement, Natural products, Nonlinear optical

Subject Categories

Organic Chemistry


A library of [alpha]-alkoxy allylstannyl ether substrates was synthesized to examine the stereochemical outcome of the unstabilized [alpha]-alkoxy allylstannyl ether [2,3] Wittig rearrangement. Well-defined stereoselectivities transpired for the generation of di- and tri-substituted olefins via the [2,3] Wittig rearrangement. Lithiation of [alpha]-alkoxy allylstannyl ethers and subsequent rearrangement produced a mixture of E and Z olefins and the reliability of the unstabilized [2,3] Wittig rearrangement was determined.

Upon completion of the unstabilized [2,3] Wittig methodology study, our next project consisted of utilizing carbohydrates, as chiral templates, toward the asymmetric synthesis of natural products. Our ultimate goal was to use this approach to install a Z disubstituted alkene in the target molecule.

The partial synthesis of (-)-discodermolide and dictyostatin, a potent immunosuppressive agent against lymphoma and breast carcinoma cells and a cytotoxic agent towards 60 different human cancer cell lines respectively, began with a common carbohydrate precursor methyl-[alpha]-D-glucopyranoside.

The preparation of a novel nonlinear optical substrate via molecular engineering of organic materials features a highly conjugated five-membered ring linker fragment. It was postulated that the molecular rigidity of this molecule thereby conformationally locks it into a planar structure thus increasing the [pi]-stacking abilities and NLO properties.


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