Novel palladium precatalysts and their application in cross- coupling reactions and copper-catalyzed enantioselective ring formation

Chapters 1 - 3. A series of easily prepared, phosphine-ligated palladium precatalysts based on the 2-aminobiphenyl scaffold have been prepared. The role of the precatalyst-associated labile halide (or pseudohalide) in the formation and stability of the palladacycle has been examined. It was found that replacing the chloride in the previous version of the precatalyst with a mesylate leads to a new class of precatalysts with improved solution stability and that are readily prepared from a wider range of phosphine ligands, including the bulky, electron-rich di-tert-butylphosphino biaryl ligands. Additionally, N-methyl- and N-phenyl analogues have been prepared. These efficacy of these precatalysts were examined in a broad range of C-C, C-N, and C-O bond-forming reactions. Chapter 4. The intramolecular hydroalkylation of di- and trisubstituted alkenes bearing a pendant alkyl bromide to form stereodefined (hetero)carbocycles is reported. The system is highly regio- and stereoselective and employs a Cu-DTBM-SEGPHOS catalyst and (dimethoxy)methylsilane as the stoichiometric reductant. This intramolecular hydroalkylation reaction provides facile access to a multitude of ring systems and its utility is further demonstrated in the enantioselective synthesis of paroxetine.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2015

Author dc:creator

• Bruno, Nicholas C. (Nicholas Charles)

Advisor dc:contributor.advisor

• Stephen L. Buchwald.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/98821

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/98821