University of Illinois Urbana-Champaign

Synthetic and chromatographic study of the spiro-lactams and spiro-lactones based on a 9',10'-dihydro-(9,10)-ethanoanthracene Diels-Alder adduct. Application of flash vacuum thermolysis towards synthesis of exo-methylene lactones and lactams

Gruber, James Vincent

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https://hdl.handle.net/2142/19026

Description

Title
Synthetic and chromatographic study of the spiro-lactams and spiro-lactones based on a 9',10'-dihydro-(9,10)-ethanoanthracene Diels-Alder adduct. Application of flash vacuum thermolysis towards synthesis of exo-methylene lactones and lactams
Author(s)
Gruber, James Vincent
Issue Date
1989
Doctoral Committee Chair(s)
Pirkle, William H.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Organic Chemistry
Language
eng
Abstract
  • Synthesis of a variety of spiro-lactams and spiro-lactones which are based on a 9$\sp\prime$,10$\sp\prime$-dihydro- (9,10) -ethanoanthracene Diels-Alder adduct has been performed. Control of relative stereochemistry at the C2 and C2, C3 carbons on the lactone ring during synthesis of the spiro-lactones has been observed and is dependent on the reaction temperature and the length of reaction time.
  • The enantiomers of both the spiro-lactones and the spiro-lactams have been shown to separate on a chiral stationary phase derived from (R)-N-(3,5-dinitrobenzoyl)phenylglycine, (R)-CSP 1. Determination of the absolute stereochemistry at the spiro-junction of the most retained enantiomer on CSP 1 for both the spiro-lactams and spiro-lactones has been done using a variety of techniques including NMR, CD, CNDO/S-CI and force field calculations. In addition, NMR concentration studies using a soluble analogue of CSP 1 have been performed and aid in determining the important interactions responsible for enantiomer recognition. Models have been developed which describe the mode of enantiomer separation of these spiro adducts on (R)-CSP 1.
  • Flash vacuum thermolysis of the spiro-lactam and spiro-lactone Diels-Alder adducts has allowed formation of a variety of exo-methylene lactams and exo-methylene lactones. In several examples, rearrangement of the exo to the more stable endo products is observed. Application of both the ability to resolve the enantiomers of a spiro-lactam precurser on CSP 1 and subsequent flash vacuum thermolysis affords an enantiomerically enriched exo-methylene lactam.
Type of Resource
text
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http://hdl.handle.net/2142/19026
Copyright and License Information
Copyright 1989 Gruber, James Vincent

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