1. Design and synthesis of phosphino-sulfonamide ligands. 2. Transition metal-catalyzed transformations of enamides and related compounds.
Contributors: University of Toronto.  Dept. of Chemistry.
Published: 2005
Language: eng
Number of pages: 122
Description: The first case of phosphino-sulfonamide-ligand has been synthesized by the reaction of readily available cyclohexane-based aziridines. It was shown through X-ray crystallography that these ligands have the trans -configuration with the cyclohexane backbone and have the ability to coordinate to the Pd center through the phosphorous atom. The deprotonation of NH functionality allows the ligand to act as a phospho-sulfonamide bidentate ligand, polarizing the nitrogen-metal bond.The intramolecular Heck cyclizations in the presence of Pd2(dba) 3/BINAP and Ag3PO4 has shown to be a convenient method to access new heterocycles in good yields. Alternate route for the formation of new heterocycles with novel properties was discovered in the presence of allyl acetate and using [PdCl(pi-allyl)]2/dppe. An attempt to understand the mechanism was made and it was realized that the reaction occurs between the enamide and the allyl-palladium complex, which then undergoes the Heck cycle to form an exo-seven-membered ring.
Notes: Source: Masters Abstracts International, Volume: 44-02, page: 0912.

Advisor: Andrei Yudin

Thesis (M.Sc.)--University of Toronto, 2005.

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