Transition metal-catalyzed alkene hydroacylation and carboacylation

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2018-01-01
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Vickerman, Kevin
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Levi M. Stanley
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Chemistry

The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

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The Department of Chemistry was founded in 1880.

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Abstract

This dissertation presents the development of new catalysts for enantioselective, rhodium-catalyzed alkene hydroacylation to form polycyclic heterocyclic ketones, the first examples of nickel-catalyzed alkene carboacylation via amide C−N bond activation, and the first examples of enantioselective, intermolecular palladium-catalyzed alkene carboacylation via ester C−O bond activation.

Chapter II describes the enantioselective synthesis of polycyclic nitrogen, oxygen, and sulfur heterocycles by rhodium-catalyzed intramolecular alkene hydroacylation. The intramolecular hydroacylation reactions generate 1,4-dihydrocyclopenta[b]indol-3(2H)- ones and 3,4-dihydrocyclopenta[b]indol-1(2H)-one in moderate-to-high yields (65-99%) with good-to-excellent enantioselectivities (84-99% ee). The catalyst system also promotes alkene hydroacylation of 3-vinylfuran-, 3-vinylbenzothiophene-, and 3-vinylthiophene-2- carboxaldehydes to generate the corresponding ketone products in moderate-to-high yields (71-91% yield) with excellent enantioselectivities (97-99% ee).

Chapter III discusses nickel-catalyzed formal carboacylation of ortho- allylbenzamides with arylboronic acid pinacol esters. The reaction is triggered by oxidative addition of an activated amide C−N bond to a Ni(0) catalyst and proceeds via alkene insertion into a Ni(II)-acyl bond. The exo-selective carboacylation reaction generates 2- benzyl-2,3-dihydro-1H-inden-1-ones in moderate to high yields (46−99%) from a variety of arylboronic acid pinacol esters and substituted ortho-allylbenzamides. These results show that amides are practical substrates for alkene carboacylation via amide C−N bond activation, and this approach bypasses challenges associated with alkene carboacylation triggered by C−C bond activation.

Chapter IV describes palladium-catalyzed formal intermolecular carboacylation of aryl benzoate esters with sodium tetraarylborates and norbornene. The reaction is triggered by oxidative addition of an activated amide C−O bond to a Pd(0) catalyst and proceeds via alkene insertion into a Pd(II)-acyl bond. The three-component intermolecular carboacylation reaction generates phenyl(3-phenylbicyclo[2.2.1]heptan-2-yl)methanones in up to 99% yield with 1:1 diastereomeric ratio and in moderate to high enantiomeric excess from a variety of aryl benzoate esters and sodium tetraarylborates. These results show that esters are practical substrates for enantioselective, intermolecular alkene carboacylation via ester C−O bond activation. This approach bypasses challenges associated with alkene carboacylation triggered by C−C bond activation and expands alkene carboacylation via carbon-heteroatom bond activation beyond twisted amides.

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Wed Aug 01 00:00:00 UTC 2018