Lizza, Joseph
(2020)
DEVELOPMENT OF THE 2,2,6,6-TETRAMETHYLPIPERIDIN-1-YLOXYCARBONYL (TEMPOC) PROTECTING GROUP AND EFFORTS TOWARDS THE TOTAL SYNTHESIS OF α-CYCLOPIAZONIC ACID.
Master's Thesis, University of Pittsburgh.
(Unpublished)
Abstract
The 2,2,6,6-Tetramethylpiperidin-1-yloxycarbonyl (Tempoc) protecting group is a new carbamate protecting group for various types of amines. Installation can be accomplished using the new reagent 4-nitrophenyl (2,2,6,6-tetramethylpiperidin-1-yl) carbonate (NPTC) under mild conditions. Tempoc is stable under strongly acidic and basic conditions, and displays orthogonal deprotection properties when used in tandem with the tert-butyloxycarbonyl (Boc) and benzyloxycarbony (Cbz) protective groups. Deprotection can be accomplished under thermolytic conditions at 135 °C, or under reductive conditions with in situ generated catalytic Cu(I). Furthermore, Tempoc has also been shown to be a useful protecting group in peptide synthesis. Protecting a broad range of biologically relevant amino esters has been accomplished in the presence of 1-hydroxybenzotriazole (HOBt) as an NPTC activator. Demonstration of Tempoc utility has been realized through the synthesis of a tripeptide fragment of Gramicidin S, a cyclic decapeptide that possesses antimicrobial activity. Unrelated, efforts toward the total synthesis of α-Cyclopiazonic acid are also discussed. The ambitious 1,3-dipolar cycloaddition of a highly substituted aziridine with relatively unactivated dipolarophiles led to interesting results that may be useful for the synthesis of other complex biologicals and natural products.
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Details
Item Type: |
University of Pittsburgh ETD
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Status: |
Unpublished |
Creators/Authors: |
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ETD Committee: |
Title | Member | Email Address | Pitt Username | ORCID |
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Committee Chair | Wipf, Peter | | | | Committee Member | Koide, Kazunori | | | | Committee Member | Curran, Dennis | | | |
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Date: |
8 June 2020 |
Date Type: |
Publication |
Defense Date: |
2020 |
Approval Date: |
8 June 2020 |
Submission Date: |
13 January 2020 |
Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
Number of Pages: |
297 |
Institution: |
University of Pittsburgh |
Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
Degree: |
MS - Master of Science |
Thesis Type: |
Master's Thesis |
Refereed: |
Yes |
Uncontrolled Keywords: |
peptides, cycloaddition, natural products |
Date Deposited: |
08 Jun 2020 15:20 |
Last Modified: |
08 Jun 2020 15:20 |
URI: |
http://d-scholarship.pitt.edu/id/eprint/38135 |
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