Knapton, Daniel Jason
(2005)
TRANSTION METAL MEDIATED CARBON-HETEROATOM AND CARBON-CARBON BOND FORMATION: STUDIES IN MULTICOMPONENT COUPLING REACTIONS AND RING-CLOSING METATHESIS.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Pd(PPh3)4 catalytically assembles sulfenamide (PhS-NR2), alkyne, carbon monoxide and diphenyl diselenide in a one-pot four component coupling reaction to yield (Z)-â-selenyl acrylamides. The reaction proceeds in good to excellent yield (60-95%) and is tolerant of a wide range of functional groups on both the nitrogen of the sulfenamide and the alkyne. Moderate selectivities ranging from 4:1 to 7:1 â-selenyl to â-sulfenyl acrylamide have been observed despite the initial concentration of 2:1 selenium to sulfur in the reaction. The chalcogeno selectivity was found to depend directly on CO pressure; increased CO pressure decreased selectivity for selenium over sulfur.The azaselenolation of carbon monoxide by sulfenamide is catalyzed by RhCl(CO)(PPh3)2 to give Se-aryl selenocarbamates. The reaction proceeds in moderate to good yield (71-89%) and exhibits a 9:1 selectivity for the formation of seleno- over thiocarbamate despite the initial 1.4:1 concentration of selenium to sulfur in the reaction. Selectivity is postulated to arise from the more favorable oxidative addition of diphenyl diselenide to rhodium relative to diphenyl disulfide. Also discussed is the effect of several transition metal complexes on the yield and selectivity of the azaselenolation reaction and our attempts to develop a transition metal catalyzed olefin azasulfenylation reaction.Imine-olefin ring-closing metathesis of á,ù imino-olefins with Schrock-type alkylidene complexes, Mo(=CHR)(=NAr)(OR')2 is discussed. Ring-closing proceeded to yield the target substrate 2H-chromene in 63% yield. Mechanistically, it was determined that the reaction operates under kinetic control via initial alkylidene-olefin metathesis followed by ring-closing alkylidene-imine metathesis.
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Details
| Item Type: |
University of Pittsburgh ETD
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| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
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| Date: |
31 January 2005 |
| Date Type: |
Completion |
| Defense Date: |
3 September 2004 |
| Approval Date: |
31 January 2005 |
| Submission Date: |
4 November 2004 |
| 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: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
multicomponent coupling reactions; palladium catalyst; ring-closing metathesis; selenium |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-11042004-134451/, etd-11042004-134451 |
| Date Deposited: |
10 Nov 2011 20:04 |
| Last Modified: |
15 Nov 2016 13:51 |
| URI: |
http://d-scholarship-dev.library.pitt.edu/id/eprint/9569 |
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