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Fluorous Mixture Synthesis (FMS) of Four Isomers of 4,8,12,-Trimethylnonadecanol and the Development of an NMR-based Method for Determining the Configurations of Polyisoprenoid Structures

Yeh, An-Hung E. (2012) Fluorous Mixture Synthesis (FMS) of Four Isomers of 4,8,12,-Trimethylnonadecanol and the Development of an NMR-based Method for Determining the Configurations of Polyisoprenoid Structures. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

The chiral polyisoprenoid motif has been identified in various natural products such as vitamin E, chlorophyll-d, and beta-mannosyl phosphomycoketide. This motif features stereocenters bearing branched methyl groups at every fourth carbon of a long alkyl chain. Due to the lack of function group, assigning the configurations of these structures is difficult.
Herein, we describe the fluorous mixture synthesis (FMS) of the 4S,8S,12S-, 4S,8R,12S-, 4R,8S,12S-, and 4R,8R,12S-trimethylnonadecanol isomers. The FMS features a new family of ultra-light fluorous O-phenyl thionocarbonate tags and employees the most efficient fluorous tagging strategy to date. The analyses of these four isomers were found to exhibit small but reliable differences in 1H and 13C NMR spectra. Furthermore, these chemical shifts of the branched methyl groups were diagnostic of relative configurations. By deducing the relative relationship between configuration and chemical shift, we developed predictions of 4,8,12,16-tetramethyltricoanol, and 4,8,12,16,20-pentamethyl-heptacosanol.

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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Yeh, An-Hung E.aey2@pitt.eduAEY2
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee MemberDay, Billy W.bday@pitt.eduBDAY
Committee MemberFloreancig, Paul E.florean@pitt.eduFLOREAN
Committee MemberNelson, Scott G.sgnelson@pitt.eduSGNELSON
Committee ChairCurran, Dennis P.curran@pitt.eduCURRAN
Date: 1 February 2012
Date Type: Publication
Defense Date: 22 November 2011
Approval Date: 1 February 2012
Submission Date: 2 December 2011
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 210
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Fluorous Mixture synthesis, FMS, polyisoprenoid, beta-Mannosyl Phosphomycoketide, MPM, O-Phenyl thionocarbonate
Date Deposited: 01 Feb 2012 16:14
Last Modified: 15 Nov 2016 13:55
URI: http://d-scholarship.pitt.edu/id/eprint/10646

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