University of Illinois Urbana-Champaign

Beta-lithiations of carboxamides: An investigation of the regio- and stereoselectivity of directed lithiations

Lutz, Gary Paul

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Description

Title
Beta-lithiations of carboxamides: An investigation of the regio- and stereoselectivity of directed lithiations
Author(s)
Lutz, Gary Paul
Issue Date
1991
Doctoral Committee Chair(s)
Beak, Peter
Department of Study
Chemistry, Organic
Discipline
Chemistry, Organic
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
  • An investigation of the diastereoselective $\beta$-metalation and of the structure of a carbanion of a $\beta$-phenyl tertiary amide has been carried out. The directed metalation has been found to occur with high diastereoselectivity and the resulting carbanion is best described as a pyramidal benzyllithium species based on $\sp{13}$C NMR evidence.
  • Secondary amides have been shown to act as directing groups for $\beta$-lithiations, and the dianion homoenolate equivalents have been shown to react with a variety of electrophiles. We have found that the remote metalations can be directed by secondary amides employing several anion stabilizing groups, and the secondary amides can undergo remote metalations when no $\alpha$-alkyl substituent is present. The rate of the directed deprotonation has been found to be dependent upon the chain length between the amide group and the anion stabilizing group. The investigation of using secondary amides as homoenolate equivalents as well as the potential and limitations of these homoenolate equivalents will be addressed.
Type of Resource
text
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http://hdl.handle.net/2142/23798
Copyright and License Information
Copyright 1991 Lutz, Gary Paul

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