Double Dehydro-Diels-Alder Reactions of 1,5-Dien-3-ynes

Date

2010

Authors

Fallon, Thomas
Robinson, Diane
Willis, Anthony
Paddon-Row, Michael
Sherburn, Michael

Journal Title

Journal ISSN

Volume Title

Publisher

Wiley-VCH Verlag GMBH

Abstract

A study was conducted to demonstrate double dehydro-diels-alder reactions of 1,5-dien-3-ynes. It was demonstrated that the reaction proceeded through two concerted cycloadditions, the first of which was proposed to be reversible. Detailed analysis revealed some of general features of the unique double diels-alder reaction. The reaction proceeded at only at high temperature, the dienophile needed to be highly activated, and yields were always low. N-Methylmaleimide (NMM) and 1,2-dicyclohexenyl acetylene 1 were selected as representative reaction partners to conduct the optimization investigations. Some of the parameters that were varied during the course of the reaction, included temperature, method of heating, and reaction stoichiometry. The effects of various radical inhibitors, solvents, and treated glassware were also investigated under the study.

Description

Keywords

Keywords: Cycloadditions; Density-functional calculations; Diels-Alder reaction; Dienophiles; Domino reactions; High temperature; Radical inhibitor; Reaction partners; Reaction stoichiometry; Acetylene; Heating; Lighting; Reaction kinetics; Stereoselectivity; Stoic Cycloaddition; Density functional calculations; Domino reactions; Stereoselectivity; Strained compounds

Citation

Source

Chemistry, A European Journal

Type

Journal article

Book Title

Entity type

Access Statement

License Rights

DOI

10.1002/chem.200902190

Restricted until

2037-12-31