The Triplex Diels-Alder Reaction: An Investigation of Enantioselectivity and Scope

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-β-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)

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Kim, Ji-In

Contributors dc:contributor

• Schuster, Gary B.

• Chemistry, Organic

Identifier

(UMI)AAI9236501

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/72268