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The synthesis and use of cyclic nitronic esters

Author: Brenda S Kesler; Scott E Denmark
Publisher: Urbana, IL. : University of Illinois, 1993.
Dissertation: Ph. D. University of Illinois at Urbana-Champaign 1993
Edition/Format:   Thesis/dissertation : Document : Thesis/dissertation : eBook   Computer File : EnglishView all editions and formats
Summary:
The Lewis acid promoted (4+2) cycloaddition of nitrostyrenes with various dienophiles was examined and several issues of selectivity were addressed. Anti diastereomers are formed exclusively in high yields in the cycloaddition with cyclic alkenes. Lewis acid complexation was examined by conducting a Hammett study which showed that electron-rich nitrostyrenes cyclize the fastest. It was shown that nitroalkenes can  Read more...
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Genre/Form: Academic theses
Material Type: Document, Thesis/dissertation, Internet resource
Document Type: Internet Resource, Computer File
All Authors / Contributors: Brenda S Kesler; Scott E Denmark
OCLC Number: 774915925
Notes: Vita.
Description: 1 pdf file
Details: System requirement: Adobe Acrobat Reader.; Mode of access: World Wide Web.
Responsibility: by Brenda S. Kesler.

Abstract:

The Lewis acid promoted (4+2) cycloaddition of nitrostyrenes with various dienophiles was examined and several issues of selectivity were addressed. Anti diastereomers are formed exclusively in high yields in the cycloaddition with cyclic alkenes. Lewis acid complexation was examined by conducting a Hammett study which showed that electron-rich nitrostyrenes cyclize the fastest. It was shown that nitroalkenes can behave as the diene component of the cycloaddition with cyclic dienes due to the effect of the Lewis acid. Finally, the selectivity of the intramolecular cycloaddition is highly dependant upon the position of sp$sp2$ centers in the tether. If that center is conjugated with the diene, syn diastereomers are afforded exclusively. The ability to employ chiral Lewis acids was examined in Chapter 3. A suitable Model System was synthesized and a survey of many Lewis acids and ligands provided only low ee's (33%) of products with a titanium trachloride/2,2$spprime$-binaphthol blend. In efforts to exploit the products obtained from these cycloadditions, we attempted to add tethered carbon radicals to the nitronic ester. Photolysis with hexamethylditin successfully formed the correct carbon-carbon bond, but products were isolated in low yield and in the wrong oxidation state. The slow addition of tributyltin hydride and AIBN afforded high yields of novel N-hydroxy N, O-acetal bicyclic compounds. Finally, various $beta$-heteroatom-substituted nitroalkenes were synthesized and successfully underwent cycloaddition with butyl vinyl ether. These nitronic esters were hydrogenated with PtO$sb2$ to afford 3-substituted pyrrolidines.

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