Recent advances in palladium-catalyzed carbon-carbon and carbon-boron bond forming processes

Chapter 1. Highly active and efficient catalyst systems derived from palladium precatalysts and monophosphine ligands for the Suzuki-Miyaura cross-coupling reaction of heteroaryl boronic acids and esters has been developed. This method allows for the preparation of a wide variety of heterobiaryls in good to excellent yields and displays a high level of activity for the coupling of heteroaryl chlorides as well as hindered aryl and heteroaryl halides. Specific factors that govern the efficacy of the transformation for certain heterocyclic motifs were also investigated. Chapter 2. A highly efficient method for the palladium-catalyzed Suzuki-Miyaura reaction of lithium triisopropyl 2-pyridylborates has been developed. Catalysts comprised of Pd2dba3 and either diaryl or dialkyl phosphine oxide supporting ligands were found to be ideal for the transformation. This report represents one of the most general systems for the cross-coupling of aryl and heteroaryl bromides and chlorides with 2-pyridyl-derived nucleophiles. Chapter 3. Catalysts comprised of Pd and dialkylmonophosphinobiaryl ligands provide highly active systems for the borylation of aryl and heteroaryl chlorides. The direct preparation of symmetrical and unsymmetrical biaryls from two aryl chlorides without the need to isolate the intermediate boronate esters is also described. Additionally, computational studies provide insight into the roles of the biaryl phosphine ligand as well as KOAc in the catalytic cycle. Chapter 4. A highly efficient method for the palladium-catalyzed borylation of aryl halides with an inexpensive and atom-economical boron source, pinacol borane, has been developed.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2008

Author dc:creator

• Billingsley, Kelvin L

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/1721.1/43777

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/43777