Frein, Jeffrey Daniel, authorRovis, Tomislav, advisor2024-03-132024-03-132007https://hdl.handle.net/10217/237739Several methods for the stereoselective formation of carbon-carbon bonds between contiguous rings where a stereogenic center is already present have been examined. The approaches investigated were: a [1,3]-oxygen to carbon rearrangement of cyclic vinyl acetals; an intermolecular enolsilane addition into an in situ generated oxocarbenium ion; an intramolecular conjugate addition of tethered alkoxy enones; and epimerization of several α-pyranyl cycloalkanones. These routes have been found to be complementary in several cases and have enabled formation of both the traps: anti and cis:anti stereoisomers in good to excellent yields and varying diastereoselectivities. The C2-C2' relative stereochemistry of the carbon-carbon bond between the adjacent rings was proven via a chemical correlation. The versatility of 1,3-dioxepines as precursors to the formation of 1,4-diols and 1,2,4-triols has been examined. The rapid synthesis of unsymmetrical 1,3-dioxepines and the installation of a 4-acetoxy substituent as a synthetic handle for further functionalization has been realized. The Lewis acid mediated addition into in situ generated oxocarbenium ions has been developed for variety of different nucleophiles. Furthermore, a highly trans -diastereoselective Heck reaction has been performed on unsymmetrical 1,3-dioxepines and their synthetic utility as precursors to the formation of 2,3,4-alkyl substituted tetrahydrofurans and 2-methoxy-4,5-alkyl substituted tetrahydrofurans have been exploited.born digitaldoctoral dissertationsengCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.adjacent ringscarbon-carbon bondsoxygen to carbon rearrangementorganic chemistryTextPer the terms of a contractual agreement, all use of this item is limited to the non-commercial use of Colorado State University and its authorized users.