Wang, Kan
(2008)
Development and Synthesis Applications of Olefin Isomerization-Claisen Rearrangement Reactions.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Iridium(I)-catalyzed olefin isomerization in bis(allyl) ethers is integrated into a generally applicable strategy for affecting highly stereoselective Claisen rearrangements. Catalyzed alkene isomerization affords allyl vinyl ethers from easily prepared di(allyl) ethers; direct thermolysis of these reaction mixtures leads to highly diastereoselective [3,3] sigmatropic rearrangements affording syn-2,3-dialkyl-4-pentenal derivatives. An easily executed strategy for realizing asymmetric variants of the isomerization-Claisen rearrangement (ICR) reactions is also described.Merging the catalytic asymmetric synthesis of di(allyl) ethers with ensuing olefin isomerization-Claisen rearrangement (ICR) reactions provides a convenient, two-step route to asymmetric aliphatic Claisen rearrangements from easily obtained starting materials. These reactions deliver the 2,3-disubstituted 4-pentenal derivatives characteristic of aliphatic Claisen rearrangements with excellent relative and absolute stereocontrol. A catalytic enantioselective synthesis of the (+)-calopin dimethyl ether demonstrates the utility of this reaction technology in asymmetric synthesis enterprises.Stereoselective quaternary all-carbon stereocenter construction is often not easily achieved from methodologies developed primarily for accessing less substituted stereogenic carbons. Olefin isomerization-Claisen rearrangement (ICR) reactions offer a strategy for recruiting the venerable Claisen rearrangement for asymmetric quaternary carbon construction. Several complementary strategies for enantioselective quaternary carbon synthesis derive directly from the ICR reaction design.
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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Unpublished |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: |
29 January 2008 |
| Date Type: |
Completion |
| Defense Date: |
29 November 2007 |
| Approval Date: |
29 January 2008 |
| Submission Date: |
20 December 2006 |
| 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: |
Olefin Isomerization-Claisen Rearrangement Reactio |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-12202006-173358/, etd-12202006-173358 |
| Date Deposited: |
10 Nov 2011 20:11 |
| Last Modified: |
15 Nov 2016 13:54 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/10439 |
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