Nickel-catalyzed asymmetric arylations of [alpha]-halocarbonyl compounds and studies of boratabenzene-containing transition metal complexes

Chapter 1 begins with a review of the current literature on cross-coupling methods to generate a-arylcarbonyl compounds, with a special emphasis on asymmetric arylations. The second section of chapter 1 describes the development of an asymmetric Negishi arylation of a-bromoketones using a nickel/pybox catalyst. The third section details the development of a Suzuki arylation of a-bromo- and a-chloroamides using aryl-(9-BBN) reagents. Both of these cross-coupling procedures are stereoconvergent, as they convert the racemic starting electrophile to an enantioenriched product. Chapter 2 describes new studies into the chemistry of boratabenzene-containing transition-metal complexes. In particular, a new method for preparing complexes bearing a diphenylphosphidoboratabenzene ligand is disclosed, starting from a transition metal-diphenylphosphide and a boracycle, which is an intermediate in the synthetic route previously used in the preparation of these complexes. In addition, the preparation and characterization of a new, tri-ortho-substituted variant of potassium diphenylphosphidoboratabenzene is described. This new species is used as a ligand in an iron complex, which is characterized. In addition, preliminary studies towards the synthesis of palladium complex bearing this new ligand are disclosed.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2010

Author dc:creator

• Lundin, Pamela M. (Pamela Marie)

• 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/1721.1/62102

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/62102