The development and application of metal-catalyzed processes for organic synthesis

Chapter 1. Copper-Catalyzed Arylation of Stabilized Carbanions A mild, general catalytic system for the synthesis of [alpha]-aryl malonates has been developed. Aryl iodides bearing a variety of functional groups can be effectively coupled to diethyl malonate in high yields using inexpensive and widely available reagents, making this a superior method to those previously described that employ copper reagents or catalysts. The functional group tolerance of the process developed makes it complementary to analogous palladium-catalyzed couplings. Importantly, a set of mild reaction conditions has been developed that minimize product decomposition, a problem that had not been addressed previously in the literature. In addition, the utilization of aryl bromides as coupling partners has been investigated, as well as the use of other classes of nucleophilic stabilized carbanions. Chapter 2. Synthesis of Oxindoles from a-Haloacetanilides via Palladium-Catalyzed C-H Functionalization We have discovered a palladium-catalyzed reaction that efficiently produces oxindoles from a-haloacetanilides through a net functionalization of an arene C-H bond. The high levels of regioselectivity observed in this cyclization obviate the need for highly functionalized aromatic substrates to effect desired ring closure. Moreover, the breadth of functional groups compatible with the reaction conditions is vastly greater than that of analogous Lewis acid-mediated processes. Extensive mechanistic work has been conducted, including kinetic isotope effect and linear free energy relationship studies.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2005

Author dc:creator

• Hennessy, Edward J. (Edward John), 1977-

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/1721.1/32521

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/32521