The Triplex Diels-Alder Reaction: An Investigation of Enantioselectivity and Scope
type: CreativeWork
description: Part I. Enantioselective triplex Diels-Alder reaction. An investigation of the enantioselective triplex Diels-Alder reaction has been performed with optically active biaryl sensitizers, (-)1,1$\sp\prime$bis(2,4-dicyanonaphthalene) and (-)1,1$\sp\prime$bis(2,10-dicyanoanthracene). Irradiation of an optically active sensitizer in non-polar solvents containing substituted trans-$\beta$-methylstyrenes and cyclic dienes yielded endo (4+2) adducts with enantioselectivity up to 23%. Our report is the first observation of an enantioselective photochemical cycloaddition reaction which is catalyzed by a chiral sensitizer. The mechanistic investigation suggests the presence of diastereomeric exciplexes. The advantages and limitations of the reaction are discussed along with the results from the mechanistic study. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)
abstract: Part I. Enantioselective triplex Diels-Alder reaction. An investigation of the enantioselective triplex Diels-Alder reaction has been performed with optically active biaryl sensitizers, (-)1,1$\sp\prime$bis(2,4-dicyanonaphthalene) and (-)1,1$\sp\prime$bis(2,10-dicyanoanthracene). Irradiation of an optically active sensitizer in non-polar solvents containing substituted trans-$\beta$-methylstyrenes and cyclic dienes yielded endo (4+2) adducts with enantioselectivity up to 23%. Our report is the first observation of an enantioselective photochemical cycloaddition reaction which is catalyzed by a chiral sensitizer. The mechanistic investigation suggests the presence of diastereomeric exciplexes. The advantages and limitations of the reaction are discussed along with the results from the mechanistic study. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)
author: Kim, Ji-In
keywords: Chemistry, Organic
date published: 2014-12-17T21:29:00Z
date modified: 2026-07-22T22:26:06Z
provider: University of Illinois - Urbana-Champaign
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Illinois at Urbana-Champaign

PropertyValue
property ID: Handle
value: http://hdl.handle.net/2142/72268