Loyer-Drew, Jennifer
(2008)
A 1,3-Dipolar Cycloaddition Approach to the Synthesis of Resiniferatoxin.
Master's Thesis, University of Pittsburgh.
(Unpublished)
Abstract
The Rh(I)-catalyzed allenic cyclocarbonylation reaction is a formal [2 + 2 + 1] cycloaddition process that has been used to gain access to 4-alkylidenecyclopentenones. Incorporation of a six-membered ring on the tether between the allene and the alkyne components allows access to a variety of [6-7-5] ring structures featured in the skeletons of various natural products, including resiniferatoxin. This thesis describes the development of two systems, each with a future synthesis of resiniferatoxin in mind. First, a model system was designed to demonstrate the compatibility of the isoxazoline moiety with the Rh(I)-catalyzed cyclocarbonylation reaction. The second investigation involved the synthesis of an asymmetrically functionalized 2-cyclohexenone in order to attempt a stereoselective 1,3-dipolar cycloaddition. The first model system successfully led to the synthesis of the unfunctionalized [6-7-5] core of resiniferatoxin via cyclocarbonylation of an isoxazoline-containing allene-yne. Unfortunately, under numerous conditions, the functionalized cyclohexenone synthesized for the second study failed to undergo [2 + 3] cycloaddition with a nitrile oxide.
Share
| Citation/Export: |
|
| Social Networking: |
|
Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
| Creators | Email | Pitt Username | ORCID  |
|---|
| Loyer-Drew, Jennifer | jal61@pitt.edu | JAL61 | |
|
| ETD Committee: |
|
| Date: |
28 September 2008 |
| Date Type: |
Completion |
| Defense Date: |
31 July 2008 |
| Approval Date: |
28 September 2008 |
| Submission Date: |
18 July 2008 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| 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: |
cycloaddition; cyclocarbonylation; daphnane; nitrile oxide; Pauson-Khand; resiniferatoxin |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-07182008-135945/, etd-07182008-135945 |
| Date Deposited: |
10 Nov 2011 19:52 |
| Last Modified: |
15 Nov 2016 13:46 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/8433 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Actions (login required)
 |
View Item |
![[feed]](/images/feed-icon-32x32.png){kind=icon}