Campus Access Only
All rights reserved. This publication is intended for use solely by faculty, students, and staff of University of the Pacific. No part of this publication may be reproduced, distributed, or transmitted in any form or by any means, now known or later developed, including but not limited to photocopying, recording, or other electronic or mechanical methods, without the prior written permission of the author or the publisher.
Date of Award
Thesis - Pacific Access Restricted
Master of Science (M.S.)
Paul H. Gross
First Committee Member
James W. Blankenship
Second Committee Member
Donald K. Wedegaertner
Prince-type cyclizations were performed with different Lewis acids to select optimal conditions, for the synthesis of a series of 4-chloro-2- phtalimidomethyl 6-methyl tetrahydropyrans and 4-chIoro-2.6- bis(phtalimido-methyl)-tetrahvdropyrans. The total yield for phtalimidomethyl products reached 92%, and for bis-phtalimido compounds 71%. An influence of reagent size and nucleophilicitv on the reaction outcome was observed, and was interpreted in terms of cationic mechanism and complex formation in the transition state. A cyclization step was also used to synthesize bicvclic compounds that can be used as precursors for the synthesis of C-oligosaccandes. Optimized eliminations of hydrogen halide by DBU in presence of LiCl yielded a mixture of 2.6-anhydro-188.8.131.52.7- penradeoxy-l-phtahmido-DA-erythrohepr-3-emto! 5b and 2.6-anhydrol, 3,4,5,7-pentadeoxy-l-phtalimido-D.L-erythrohept-4-enitoI 6b in 79°a yield for the isomeric mixture. Epoxidation of this alkene mixture by a newly developed method with urea-hydrogen peroxide complex and trifluoroaceric anhydride afforded a mixture of epoxy-2-methvl-6- phtalimidomethyl tetrahydropyrans in 92% total yield. Epoxides were cleaved by aq. CF3COOH to give a mixture of dihydroxy-2-methyi-6- phtalimi dome by 1 tetrahydropyrans with an overall yield of 74% from the mixture of 5b/6b. The regioisomers were separated and deprotected by a newly developed method, and were oxidized to produce partially functionalized racemic aminomethyl C-glycopyranosides. One of the isomers was characterized as an N-acetyl-di-O-acetyl derivative and as a NBoc di-O-acetyl derivative, because this isomer was very hygroscopic.
It was also found that transallylation occurred between acetal and homoallylic alcohol during the cyclization step. A new method for the synthesis of homoallylic alcohols from acetals was developed on the basis of this observation. Homoallylic alcohols, l-Benzyloxv-4-penten-2-ol 19. 1- Phenyl-4-pentene-2-ol 18 and BPhtalimido-4-pentene-2-ol 1β were synthesized by a new method with yields of 40%. 61 % and / i % respectively. The as yet unoptimized method allows to synthesize homoallylic alcohols from unstable aldehydes.
Gremyachinskiy, Dmitriy Y.. (2000). Total Synthesis of Aminomethyl C-glycosides. University of the Pacific, Thesis - Pacific Access Restricted. https://scholarlycommons.pacific.edu/uop_etds/3765
To access this thesis/dissertation you must have a valid pacific.edu email address and log-in to Scholarly Commons.
If you are the author and would like to grant permission to make your work openly accessible, please email