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oai:mountainscholar.org:10217/2428892026-01-29T21:33:11Zcom_10217_100532com_10217_100000com_10217_100367com_10217_100303col_10217_100538col_10217_100368

Sebahar, Holly Lynn, author Hegedus, Louis, advisor 2026-01-23T17:29:55Z 2002 ETDF_2002_Sebahar_3064011.pdf https://hdl.handle.net/10217/242889 https://doi.org/10.25675/3.025746 Studies were conducted towards advancing a trans-epoxy alcohol, derived from an amino-substituted cyclobutanone, to trehalamine. Efforts to manipulate the epoxy alcohol under standard conditions were hindered by the extraordinary propensity of the system to undergo the Payne rearrangement and the steric environment shielding both the hydroxyl group and the epoxide. Metal-catalyzed allylic substitution reactions of allylic esters containing chiral quaternary and tertiary centers adjacent to the allyl system were examined. Reaction with stabilized nucleophiles led to exclusive attack at the less hindered allylic terminus and the stereoselectivity varied with the bidentate ligand used but favored retention. The yields and reaction times were improved with the use of microwaves. Application of standard conditions for transmetallation afforded starting material or decomposition. Conversely, vinyl and phenylstannatranes reacted cleanly and gave the opposite regio- and stereoselectivity than was observed with stabilized anions. Catalysts containing metals other than palladium were completely unreactive and led to recovered starting material. born digital doctoral dissertations English eng Colorado State University. Libraries 2000-2019 Copyright 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. Per 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. organic chemistry Studies towards the synthesis of trehalamine and the effect of adjacent chiral tertiary and quaternary centers on the metal-catalyzed allylic substitution reaction Text Doctor of Philosophy (Ph.D.) Doctoral Chemistry Colorado State University This Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). open.access