Exploration of the inverse-electron-demand Diels-Alder (IEDDA) reaction. Rapid access to benzocoumarins via IEDDA-driven domino reactions of coumarin-fused electron-deficient dienes with electron-rich dienophiles

Pottie, Ian R. (2002) Exploration of the inverse-electron-demand Diels-Alder (IEDDA) reaction. Rapid access to benzocoumarins via IEDDA-driven domino reactions of coumarin-fused electron-deficient dienes with electron-rich dienophiles. Doctoral (PhD) thesis, Memorial University of Newfoundland.

[img] [English] PDF - Accepted Version
Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission.

Download (7Mb)

Abstract

Chapter 1 overviews the general concepts of the Diels-Alder reaction, and particular attention is given to the inverse-electron-demand Diels-Alder reaction (IEDDA). Examples of all-carbon diene systems that contain electron-withdrawing groups at their 1- and 3-positions and their IEDDA reactivity are described. -- Chapter 2 presents the synthesis of a coumarin-fused diene that was produced in a single step. An oxidative cleavage of this diene produces 3-formylcoumarin, which can be used in the Homer-Wadsworth-Emmons reaction or the Knoevenagel condensation to afford other coumarin-fused dienes. -- Chapter 3 presents the IEDDA reactivity of methyl (E)-3-(2-oxo-2H-chromen-3-yl)acrylate with electron-rich dienophiles. Enamines undergo an IEDDA-driven domino reaction to produce benzocoumarins. The reaction procedure can be simplified by generating the dienophile in situ. -- Chapter 4 details the methodology development of the IEDDA-driven domino reactions. The methodology was used to synthesize a subunit of a new heterokekulene and efficiently generate benzocoumarins from the appropriate phenols. Preliminary results for producing azabenzcoumarins are also discussed. -- Chapter 5 contains details of a concise, high yielding total synthesis of a naturally occurring benzocoumarin by applying the methodology developed in Chapter 4. An IEDDA-driven domino reaction constitutes the key step of the synthesis.

Item Type: Thesis (Doctoral (PhD))
URI: http://research.library.mun.ca/id/eprint/11273
Item ID: 11273
Additional Information: Bibliography: leaf 375.
Department(s): Science, Faculty of > Chemistry
Date: 2002
Date Type: Submission
Library of Congress Subject Heading: Diels-Alder reaction; Diolefins.

Actions (login required)

View Item View Item

Downloads

Downloads per month over the past year

View more statistics