Casarez, Anthony David
(2005)
RHODIUM(I)-CATALYZED CYCLOISOMERIZATION OF NITROGEN TETHERED ENE-ALLENES: FORMATION OF TETRAHYDROAZEPINES.
Master's Thesis, University of Pittsburgh.
(Unpublished)
Abstract
Abstract: A novel cycloisomerization process involving nitrogen-tethered 1,6-ene-allenes has been realized. Subjecting ene-allene 9 to rhodium biscarbonyl chloride dimer produces tetrahydroazepine 10 in moderate to high yields. Substituting the allene moiety with the bulky tert-butyl-group (R4 = t-Bu), while employing a trans-alkene tether, afforded the corresponding azepines in the highest yields. This formal Alder-ene transformation tolerated not only a variety of alkyl-substituents on both the alkene and allene portions but also silyl-[R2 = SiMe3, SiMe2Bn; R4 = Si(i-Pr)3] and phenyl-(R2 = Ph, R4 = Ph) substituents. A deuterium labeling study aided in the postulation of two possible mechanisms for this cycloisomerization. During the course of this investigation, a novel carbon monoxide insertion reaction was observed. Our findings to date are reported and discussed herein.
Share
Citation/Export: |
|
Social Networking: |
|
Details
Item Type: |
University of Pittsburgh ETD
|
Status: |
Unpublished |
Creators/Authors: |
Creators | Email | Pitt Username | ORCID  |
---|
Casarez, Anthony David | adc9@pitt.edu | ADC9 | |
|
ETD Committee: |
|
Date: |
7 June 2005 |
Date Type: |
Completion |
Defense Date: |
24 November 2004 |
Approval Date: |
7 June 2005 |
Submission Date: |
15 April 2005 |
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: |
azepine; cycloisomerization; ene-allenes; rhodium |
Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-04152005-164304/, etd-04152005-164304 |
Date Deposited: |
10 Nov 2011 19:37 |
Last Modified: |
15 Nov 2016 13:40 |
URI: |
http://d-scholarship.pitt.edu/id/eprint/7190 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Actions (login required)
 |
View Item |