Computational study on the origins of asymmetric induction in Pd-catalyzed cross-coupling reactions and suggestions for improvements thereupon

The origins of asymmetric induction in the Suzuki-Miyaura cross coupling reaction are investigated computationally with density functional theory. Monophosphine-bound palladium complexes are analyzed in the context of oxidative addition to aryl halides, and ligands are explored in terms of steric and electronic effects relevant to oxidative addition. As one of the most successful ligands to date for the asymmetric Suzuki reaction, KenPhos is given substantial attention and subjected to detailed structural analysis. The analysis leads to proposals for new ligands that may enhance the asymmetry of oxidative addition, and some initial synthetic work in that capacity is presented Thesis Supervisor: Professor Stephen L. Buchwald

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

• Huhn, Richard A. (Richard Andrew)

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/1721.1/42916

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/42916