University of Illinois Urbana-Champaign

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

Kim, Ji-In

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Description

Title
The Triplex Diels-Alder Reaction: An Investigation of Enantioselectivity and Scope
Author(s)
Kim, Ji-In
Issue Date
1992
Doctoral Committee Chair(s)
Schuster, Gary B.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
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)
  • Part II. Triplex Diels-Alder reaction with acetylenic dienophiles. An investigation of triplex Diels-Alder reaction has been carried out with sensitizers, 1,4-dicyanonaphthalene or 2,6,9,10-tetracyanoanthracene. Irradiation of a sensitizer in non-polar solvents containing acetylenic dienophiles and dienes yielded cycloaddition products. Results showed that either (4+2) or (2+2) cycloadducts are formed depending on whether the diene is cyclic or acyclic. Through product and photophysical studies, the scope and limitations of triplex Diels-Alder reaction with acetylenic dienophiles were examined.
Graduation Semester
1992
Type of Resource
text
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http://hdl.handle.net/2142/72268

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