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(Unpublished)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.
Share
| Citation/Export: |
|
| Social Networking: |
|
Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
| Title | Member | Email Address | Pitt Username | ORCID |
|---|
| Committee Chair | Wipf, Peter | | | | | Committee Member | Koide, Kazunori | | | | | Committee Member | Curran, Dennis | | | |
|
| 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 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Actions (login required)
 |
View Item |
![[feed]](/images/feed-icon-32x32.png){kind=icon}