Manganese-catalyzed carbonylation of alkyl iodides
Name
589162702-MIT.pdf
Description
Full printable version
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4.61 MB
Format
Adobe PDF
Checksum (MD5)
25369b4aaf2fa005bcc3344eb6fb5dff
Author(s)
Westerhaus, Felix Alexander
Advisor(s)
Stephen L. Buchwald.
Date Issued
2009
Publisher
Massachusetts Institute of Technology
Abstract
The palladium-catalyzed cross-coupling of aryl bromides with zirconocene-benzyne complexes has been investigated by S.L. Buchwald and coworkers. This method allows the formation of substituted biphenyls and terphenyls, however only two ortho-substituents are tolerated in this transformation. The studies reportd herein aimed at the synthesis of tri- and tetra substituted biaryls, since they are important precursors to biaryl phosphine ligands. The project did not succeed due to stability problems of the formed substituted zirconium biaryl. A general method for the manganese-catalyzed carbonylation of alkyl iodides while using a variety of nucleophiles was developed. The method concerns the alkoxy and amino carbonylation as well as the use of more unconventional nucleophiles such as thiols, azide and hydride. The method employs alkyl iodides although bromides are also feasible substrates through in situ Finkelstein reaction with catalytic to substoichiometric amounts of sodium iodide. The functional group tolerance is high and the conditions for the transformation are mild using only 40 psi of carbon monoxide pressure and temperatures between r.t. and 90°C for more difficult cases.
Description
Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2009.
Vita. Cataloged from PDF version of thesis.
Includes bibliographical references (p. 121-125).
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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