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Palladium Reagents and Catalysts : New Perspectives for the 21st Century
ISBN: 0470850329
Title: Palladium Reagents and Catalysts : New Perspectives for the 21st Century
Author: Jiro Tsuji
Publisher: John Wiley & Sons


http://muchong.com/bbs/viewthread.php?tid=243678&fpage=1



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[ Last edited by daiqiguang on 2007-5-31 at 07:21 ]
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Palladium

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Palladium-Catalyzed Intermolecular -Arylation of Zinc Amide Enolates under Mild Conditions



Takuo Hama, Darcy A. Culkin, and John F. Hartwig;J. Am. Chem. Soc.; 2006; 128;128(15) pp 4976 - 4985; (Article) DOI: 10.1021/ja056076i.

Abstract:

The intermolecular -arylation and vinylation of amides by palladium-catalyzed coupling of aryl bromides and vinyl bromides with zinc enolates of amides is reported. Reactions of three different types of zinc enolates have been developed. The reactions of aryl halides occur in high yields with isolated Reformatsky reagents generated from -bromo amides, with Reformatsky reagents generated in situ from -bromo amides, and with zinc enolates generated by quenching lithium enolates of amides with zinc chloride. This use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of amide arylation. The reactions occur at room temperature or 70 C with bromoarenes containing cyano, nitro, ester, keto, fluoro, hydroxyl, or amino functionality and with bromopyridines. Moreover, the reaction has been developed with morpholine amides, the products of which are precursors to ketones and aldehydes. The arylation of zinc enolates of amides was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive, dimeric, Pd(I) complex {[P(t-Bu)3]PdBr}2.
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2Â¥2006-05-11 09:15:32
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Room Temperature Palladium-Catalyzed Intramolecular Hydroamination of Unactivated Alkenes



Forrest E. Michael* and Brian M. Cochran;J. Am. Chem. Soc.; 2006; 128; pp 4246 - 4247.

Abstract:

A mild and facile Pd-catalyzed intramolecular hydroamination of unactivated alkenes is described. This reaction takes place at room temperature and is tolerant of synthetically useful acid-sensitive functional groups. The formation of hydroamination products rather than oxidative amination products is due to the use of a tridentate ligand on Pd which effectively inhibits -hydride elimination.
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3Â¥2006-05-11 09:18:44
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Microwave-Promoted Aminocarbonylation of Aryl Iodides, Aryl Bromides, and Aryl Chlorides in Water



Xiongyu Wu, Jenny K. Ekegren, and Mats Larhed; Organometallics; 2006; 25; pp 1434-1439..

Abstract:

Fast and direct methods have been developed for the small-scale carbonylative preparation of benzamides from aryl iodides, bromides, and chlorides in pure water. The reactions proceed by palladium catalysis using noninert conditions, solid Mo(CO)6 as the CO source, and controlled microwave superheating. Within 15 min of microwave processing, more than 90 aminocarbonylations were successfully performed in useful to excellent yields employing both primary and secondary amines. Using appropriate ratios of starting amines and aryl halides, the competing hydroxycarbonylation reaction was suppressed and only trace amounts of the corresponding carboxylic acids were detected. Based on this aqueous carbonylation, a facile preparation of a novel HIV-1 protease inhibitor was achieved.

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