Physical Sciences and Mathematics Commons^™

Nucleophilic Carbon-Carbon Bond-Forming Reactions Of 2-Methylenetetrahydropyrans, Laura Jean Bateman

Chemistry - Dissertations

Reactions with 2-methylenetetrahydropyrans are underutilized in the literature, especially with respect to general methods demonstrating their nucleophilic nature. This work provides three general methods toward the synthesis of 2-β-oxygenated pyranyl substrates, which are key structural components of many biologically active polyketides and natural products.

The use of exocyclic enol ethers as nucleophiles was first demonstrated as a general process in three-component coupling reactions with secondary nucleophiles. The 2-β-hydroxy tetrahydropyran products were obtained in good to excellent yields through promotion with stoichiometric levels of titanium(IV) chloride at reduced temperatures. Only activated aldehydes or ketones worked as efficient coupling partners for this …