University of Illinois Urbana-Champaign

The Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides

Rollinson, Susan Lynn Wells

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Description

Title
The Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides
Author(s)
Rollinson, Susan Lynn Wells
Issue Date
1980
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
Language
eng
Abstract
  • Phenylselenenyl esters (methyl esters of 2-phenylselenenylhexadecanoic, 2-phenylselenenyloctadecanoic, and 2-phenylselenenyl-13-tetradecadienoic acids) were used as acrylate (alpha)-anion synthons in aldol addition reactions. The last acid above, bearing the terminal double bond, was synthesized by displacing the (omega)-bromide from methyl 11-bromo-2-phenylselenenylundecanoate by allyllithium. The other (alpha)-phenylselenenyl esters were made by quenching their lithium enolates with phenylselenenyl chloride. Addition to acrolein, followed by oxidation and selenoxide elimination gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propenyl group at the (alpha)-carbon. Similarly, addition to propargylaldehyde followed by oxidative work-up gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propynyl group at the (alpha)-carbon.
  • Hydrolysis of the olefinic esters to the corresponding carboxylic acids followed by lactonization (iodine or phenylselenenyl chloride) and hydrogenolysis (tri-n-butyltin hydride) gave (alpha)-alkylidene-(beta)-hydroxy-(gamma)-methyl-(gamma)-butyrolactones which are known natural products (litsenolides, dihydromahubanolides). Hydrolysis of the acetylenic esters to the corresponding carboxylic acids, followed by lactonization (mercuric trifluoroacetate or sodium bicarbonate) gave (alpha)-alkylidene-(beta)-hydroxy-(gamma)-methylene (gamma)-butyrolactones which are also known natural products (obtusilactones, mahubanolides). One of these, obtusilactone, the (gamma)-methylene lactone with the (alpha)-11-dodecenylidene moiety, has been reported to be cytotoxic.
Graduation Semester
1980
Type of Resource
text
Permalink
http://hdl.handle.net/2142/67250

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