Palladium-catalyzed C-C, C-N and C-O bond formation

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.

Saved in:
Bibliographic Details
Main Author: Huang, Xiaohua, 1973-
Other Authors: Stephen L. Buchwald.
Format: Thesis
Language:eng
Published: Massachusetts Institute of Technology 2006
Subjects:
Online Access:http://hdl.handle.net/1721.1/29639
id mit1721.1-29639
record_format dspace
spelling mit1721.1-296392019-04-10T12:44:54Z Palladium-catalyzed C-C, C-N and C-O bond formation Palladium-catalyzed carbon-carbon, carbon-nitrogen and carbon-oxygen bond formation Huang, Xiaohua, 1973- Stephen L. Buchwald. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003. Vita. Includes bibliographical references. New methods for Pd-catalyzed cross-coupling reactions of aryl halides or arenesulfonates are described. Key to the success of these transformations is the proper choice of ligand and reaction conditions. Palladium catalysts supported by bulky, monodentate phosphine ligands with a biaryl backbone or the bidentate ligand, Xantphos, effectively promote the formation of ca-aryl carbonyl compounds. Base-sensitive functional groups are better tolerated when a weak base, such as K3PO4, is used. One of the most difficult transformations in Pd catalysis, the intermolecular C-O bond formation between primary alcohols and electron-neutral or even electron-rich aryl halides, was effectively promoted by the use of a new generation of ligands, 3-methyl-2-di-t-butylphosphinobiaryl. The one-step synthesis of ligands from cheap starting materials, as well as the mild reaction conditions employed for the coupling reactions, enables the practical use of Pd catalysis to access aryl alkyl ethers for the first time. Continuing study of Pd-catalyzed C-N bond-forming processes using biaryl monophosphine ligands led to the discovery of a structural derivative of these ligands, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl. This ligand, in combination with a Pd source, produces a catalyst system with both a greater degree of activity and of stability than those that use our previous ligands. Substrates that were not amenable to Pd catalysis previously are reexamined using this new catalyst system, and excellent results are obtained. by Xiaohua Huang. Ph.D. 2006-03-24T16:10:30Z 2006-03-24T16:10:30Z 2003 2003 Thesis http://hdl.handle.net/1721.1/29639 53399636 eng 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. http://dspace.mit.edu/handle/1721.1/7582 216 leaves 6636696 bytes 6636505 bytes application/pdf application/pdf application/pdf Massachusetts Institute of Technology
institution DSpace@MIT
collection DSpace
language eng
topic Chemistry.
spellingShingle Chemistry.
Huang, Xiaohua, 1973-
Palladium-catalyzed C-C, C-N and C-O bond formation
description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.
author2 Stephen L. Buchwald.
author_facet Stephen L. Buchwald.
Huang, Xiaohua, 1973-
format Thesis
author Huang, Xiaohua, 1973-
author_sort Huang, Xiaohua, 1973-
title Palladium-catalyzed C-C, C-N and C-O bond formation
title_short Palladium-catalyzed C-C, C-N and C-O bond formation
title_full Palladium-catalyzed C-C, C-N and C-O bond formation
title_fullStr Palladium-catalyzed C-C, C-N and C-O bond formation
title_full_unstemmed Palladium-catalyzed C-C, C-N and C-O bond formation
title_sort palladium-catalyzed c-c, c-n and c-o bond formation
publisher Massachusetts Institute of Technology
publishDate 2006
url http://hdl.handle.net/1721.1/29639
_version_ 1654030813629513728
score 14.09242

CIC - Centro de Información y Conocimiento Johannes Gutenberg ®