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Total Synthesis of the Reported Structure of Neaumycin B / Jiaming Ding.

Dissertations & Theses @ University of Pennsylvania Available online

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Format:
Book
Thesis/Dissertation
Author/Creator:
Ding, Jiaming, author.
Contributor:
University of Pennsylvania. Chemistry, degree granting institution.
Language:
English
Subjects (All):
Chemistry.
Pharmaceutical sciences.
Biochemistry.
Bioengineering.
Chemistry--Penn dissertations.
Penn dissertations--Chemistry.
Local Subjects:
Chemistry.
Pharmaceutical sciences.
Biochemistry.
Bioengineering.
Chemistry--Penn dissertations.
Penn dissertations--Chemistry.
Physical Description:
1 online resource (392 pages)
Distribution:
Ann Arbor : ProQuest Dissertations & Theses, 2023
Contained In:
Dissertations Abstracts International 85-08B.
Place of Publication:
[Philadelphia, Pennsylvania] : University of Pennsylvania, 2022.
Language Note:
English
Summary:
Neaumycin B is a macrocyclic polyketide natural product that has shown potent activity against U87 human glioblastoma cell. In this dissertation, the first stereoselective total synthesis of the reported structure of Neaumycin B is reported in a 2.3% overall yield on 90-mg scale. The synthesis features a convergent strategy via union of smaller fragments. Key transformations in the total synthesis involves a gram-scale nickel-catalyzed reductive cross-coupling/spiroketalization to construct the axial/equatorial (A/E) spirocyclic core of Neaumycin B, and a sequential Carreira asymmetric alkynylation/trans-reduction to forge the linear southern hemisphere of the macrocycle.Comparison of the NMR data of synthetic Neaumycin B and that of the natural sample, however, displayed significant deviations. In addition, the reported synthetic Neaumycin B showed no anti-proliferative activity against Glioblastoma cells. The stereo structures that span C3-C6, C8-C14 and C20- C41 of synthetic Neaumycin B were unambiguously confirmed by X-ray crystallography, and C7 stereogenicity was individually verified via Mosher ester analysis. Based on the evidences above, we are confident that synthetic Neaumycin B I prepared as described in this dissertation matches the reported structure, and a future revision on the proposed structure of this natural product will be necessary.
Notes:
Source: Dissertations Abstracts International, Volume: 85-08, Section: B.
Advisors: Smith, Amos B., III; Petersson, E. James; Committee members: Winkler, Jeffrey D.; Huryn, Donna; Trauner, Dirk.
Department: Chemistry.
Ph.D. University of Pennsylvania 2023.
Local Notes:
School code: 0175
ISBN:
9798381510119
Access Restriction:
Restricted for use by site license.

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