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Rollinson, Susan Lynn Wells 2014-12-13T20:11:06Z 2014-12-13T20:11:06Z 10000-01-01 1980 1980 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. Made available in DSpace on 2014-12-13T20:11:06Z (GMT). No. of bitstreams: 1 8108644.pdf: 3438344 bytes, checksum: d807d264c2b9b0059aa1476aa5e4aa10 (MD5) Previous issue date: 1980 Embargo set by: Seth Robbins for item 67428 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 126 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980. http://hdl.handle.net/2142/67250 (UMI)AAI8108644 eng Chemistry, Organic The Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.