(N-heterocyclic-carbene)Copper(I)-catalyzed carbon-carbon bond formation using carbon dioxide
Name
174969988-MIT.pdf
Description
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Checksum (MD5)
205855d24265d809c77c7f26036c9767
Author(s)
Sirokman, Gergely
Advisor(s)
Joseph P. Sadighi.
Date Issued
2007
Publisher
Massachusetts Institute of Technology
Abstract
This thesis presents work towards the development of a new catalytic C-C bond forming reaction. Alkynes and olefins insert into [(IPr)CuH]2 (IPr = N,N-bis-(2,6-diisopropylphenyl)-1,3-imidazol-2-ylidene) to give copper vinyl and copper alkyl complexes. These copper complexes insert CO2 into the Cu-C bond to form copper acrylate and copper carboxylate complexes. Acrylic and carboxylic acids can be isolated by hydrolysis. A catalytic cycle based on (IPr)copper(I) was developed. Alkynes undergo reductive carboxylation to give acrylic acids in moderate yields. Unexpected interactions between several components of the catalytic system led to a number of side reaction, most importantly between [(IPr)CuH]2 and the product silyl acrylate. The use of silylcarbonate salts to desylilate the product enhanced yield. In addition, silylcarbonates can also serve as a source of CO2.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007.
Vita.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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