Degree Type

Dissertation

Date of Award

2018

Degree Name

Doctor of Philosophy

Department

Chemistry

Major

Organic Chemistry

First Advisor

Levi M. Stanley

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.

Copyright Owner

Kevin Leon Vickerman

Language

en

File Format

application/pdf

File Size

158 pages

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