Development and application of transition metal-catalyzed cross-coupling reactions

Chapter 1. PALLADIUM-CATALYZED REGIOSELECTIVE HYDRODEBROMINATION OF DIBROMOINDOLES A novel approach to the selective preparation of 4-bromoindoles has been developed via a Pd-catalyzed reaction. A variety of 4,6-dibromoindoles, which are prepared via Cu-catalyzed chemoselective C-N bond-forming reaction and subsequent Fischer indole cyclization, are transformed to 4-bromoindoles with high regioselectivity using a catalytic Pd(OAc)2/rac-BINAP system. This new method allowes for the preparation of a variety of 2,3,4,5-polysubstituted indoles from aryl halides. Chapter 2. ENANTIOSELECTIVE SYNTHESIS OF INDOLODIOXANE (S)- U86192A The enantioselective synthesis of the antihypertensive agent indolodioxane (S)-U86192A is described. The 4-bromo-5-alkoxy indole, a key intermediate of the synthesis, is prepared according to the new approach developed in chapter 1. The other noteworthy metal-catalyzed transformations, which play a crucial role in the synthesis, include a palladium-catalyzed intramolecular C-O bond-forming reaction to construct the 1,4-benzodioxane structure. The optical purity of U86192A arises from the use of cobalt-catalyzed enantioselective epoxide ring-opening reaction.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2004

Author dc:creator

• Chae, Junghyun, 1973-

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/1721.1/17735

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/17735