The development of palladium-catalysts for organic synthesis

Chapter 1. Suzuki-Miyaura coupling reactions of aryl and heteroaryl halides with aryl-, heteroaryl and vinyl boronic acids proceed in very good to excellent yield with the use of 2-(2',6'-dimethoxybiphenyl)-dicyclohexylphosphine, SPhos. Additionally, a comparison of the reactions with SPhos and with 2- (2',4',6'-triisoprc'pylbiphenyl)-diphenylphosphine is presented that is informative in determining the relative importance of ligand bulk and electron-donating ability in the high activity of catalysts derived from ligands of this type. Further, when the aryl bromide becomes too hindered, an interesting C-H bond functionalization-cross-coupling sequence intervenes to provide product in high yield. Chapter 2. The direct transformation of aryl bromides into the corresponding Weinreb amides via Pd-catalyzed aminocarbonylation at atmospheric pressure is described. Electron-deficient, -neutral and -rich aryl bromides were all efficiently transformed to product. Furthermore, the process tolerates a wide variety of functional groups, is mild, and is operationally simple. Chapter 3. A general, functional group tolerant, and mild system for the Pd-catalyzed Heck carbonylation of aryl chlorides into the corresponding benzamides 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

2007

Author dc:creator

• Martinelli, Joseph R

Advisor dc:contributor.advisor

• Stephen J. 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/1721.1/39738

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/39738