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Palladium

荣誉版主 (著名写手)

火虫

[交流] [讨论]关于金属Pd催化的有机反应

如题!!!!!!!

欢迎大家多多发言

叫更多人来关注这个金属吧!


就是Palladium

........

我抛砖引玉...........



推荐关于Pd催化的专著一本

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



为免网络侵权纠纷和给小木虫带来不必要的麻烦,,本人只转帖国外论坛发布的下载地址,请理解!!本人没有上传这本书,!!这书只供个人学习,研究或者欣赏他人发表的作品!!
Download Link:

http://rapidshare.de/files/20135 ... wiley_2004.pdf.html

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

至尊木虫 (正式写手)

我觉得市场是大家的,他最终属于强者!所以我公布我的目的化合物:烷基环己基环己酮[是对位,反式]。我的原料是烷基环己基苯酚。遇到的困难是自制的催化剂稳定性不够。多次用酮的纯度达不到98%。
希望得到高人指点!!
25楼2006-05-14 21:15:19
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普通回帖

Palladium

荣誉版主 (著名写手)

火虫

这是美国耶鲁大学John F. Hartwig教授(我的偶像之一)的一篇近作!


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.
我是个好人,别人都这么说!嘿嘿!
2楼2006-05-11 09:15:32
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Palladium

荣誉版主 (著名写手)

火虫

这是发表在JACS上另外关于Pd催化的近作!


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.
我是个好人,别人都这么说!嘿嘿!
3楼2006-05-11 09:18:44
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Palladium

荣誉版主 (著名写手)

火虫

★ ★
berlin(金币+2):继续努力了,推荐的书籍不错
这是一篇用微波炉做的反应,我直觉应该上JACS!


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.

我是个好人,别人都这么说!嘿嘿!
4楼2006-05-11 09:25:13
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liuluzcj

至尊木虫 (正式写手)

1

用钯做催化剂有1偶联反应2氢化3氧化4氢化后氧化
我最近在做一个苯酚制环己酮的实验涉及3个亿的产值。遇到主要问题是钯催化剂的活性,英国一公司的催化剂很好用,可自己做的会有定量环己醇副产。请教楼主我要注意啥?
5楼2006-05-11 11:05:46
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Palladium

荣誉版主 (著名写手)

火虫

引用回帖:
Originally posted by liuluzcj at 2006-5-11 11:05 AM:
用钯做催化剂有1偶联反应2氢化3氧化4氢化后氧化
我最近在做一个苯酚制环己酮的实验涉及3个亿的产值。遇到主要问题是钯催化剂的活性,英国一公司的催化剂很好用,可自己做的会有定量环己醇副产。请教楼主我要注意 ...

你有英国这家公司的催化剂吗?

你是用相同的催化剂,还是自己做的(分子式结构)不一样的催化剂呢?
我是个好人,别人都这么说!嘿嘿!
6楼2006-05-11 11:44:25
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liuluzcj

至尊木虫 (正式写手)

谢楼主关心!就是10-5%Pd/C催化剂呀,用他去氢化苯酚制环己酮。我现没了英国的催化剂,但以前用过。
7楼2006-05-11 15:04:24
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paracyclophane

荣誉版主 (著名写手)

虫儿飞~~

1

palladium可是heck反应专家哦,JACS、Angew、。。。。
学习ing!!

liuluzcj说的那家公司是Johnson Matthey?
若您能够保证连续灌上1200个月的水,那您准活到100岁!!
8楼2006-05-11 17:18:44
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sunic

木虫 (著名写手)

道法自然

1

路过,支持!
不怕太阳晒,也不怕风雨狂,就怕先生骂我懒啊,回家无颜见爹娘
9楼2006-05-11 18:13:39
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cjhzcw

银虫 (初入文坛)

1

国外的钯催化剂好贵啊!
对于自己做钯催化剂,楼主有什么高招吗??
10楼2006-05-11 21:17:14
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