文献报告：Zn-Mediated Reactions as Reagents and Catalysts
这是我个人在2005年初做的45分钟文献报告，我准备了大概2个月的时间（这期间还得teaching和做实验为qualifying exam准备）。将近两年的时间过去了，这个文件再也没打开过。放在计算机里，除非将来做学问需要用到这类反应，否则这个文件的价值也就趋近于“zero”。所以，我斗胆拿出来分享。因为在这个计算机上，只有一稿，也不知道是否是最后的版本，如果上面有什么错误的，请原谅。还有一点，我所有的帖子都不设置限制，这么做的目的是尽可能让大家能够自由的浏览。当然，你受益了，那是一种价值，虽然对我没有价值，但在你受益之后，也会考虑到怎么让自己也作出对他人有益的事情。这也就是这个chem8作为一个community的价值。
（请原谅，我老喜欢说这些大话，也许是因为我们中国现实中太缺乏了这些价值，所有有点惺惺相惜的感慨）
我们学校规定，在进行qualifying exam 之前，每个学生都要做departmental student seminar。有机专业的题目是教授出，学生从中选一个。别的专业都是自定，然后自己选时间做报告。我的专业无机，而我对有机金属比较感兴趣，于是我就选了一个有机金属锌的课题。这个领域做得最好的，目前是Prof. Dr. Paul Knochel，曾经是我们学校的教授，后来回德国去了。
[url]http://www.knochel.cup.uni-muenchen.de/[/url]
这里我把其中一张slide copy过来作为介绍，其他具体的内容我就不多说了，感兴趣的人可以下载附件来看。
History of Organozinc Development
First zinc reagent, diethylzinc, prepared by Frankland, 1948
Organozinc compounds were examined in a systematic way before 1888 towards organic eletrophiles like acid chlorides, aldehydes, or esters (Reformatsky reaction)
In the first half 20th century, only Reformatsky reaction was routinely used
In 1942, Hunsdiecker prepared several functionalized zinc reagents, RO2C(CH2)nZnI (n > 5)
In 1960s, Wittig and Jautelet reported the preparation of new functionalized zinc reagents PhCO2CH2ZnI and PhCO2(CH2)4ZnI. Gaudemar prepared allyic zinc reagents in high yield, an ideal source of a nucleophilic allylic anion
Iodomethylzinc iodide was prepared in 1970s, a very useful reagent in cyclopropanation reaction (Simmon-Smith reaction)
In 1980s, chemistry of homoenolates pioneered by Nakamura and Kuwajima, and cross-coupling reaction of organozincs with organic halides (Negishi coupling)
In 1990s, the use of highly reactive zinc (Rieke zinc) allowed the preparation of zinc reagents from otherwise unreactive organic substrates, such as aryl iodides and aryl bromides
回复 #1 agostic 的帖子
谢谢你 的帖子,我正对锌赶到有点兴趣呢. 好东东，受教了，多谢agostic 谢了！！！ 非常感谢 谢谢分享 :) hao dong dong 谢谢 谢谢！ 非常感谢 十分感激 多谢奉献 A short story about reformatsky reaction:About 15 years ago, my boss had a paper about reformatsky reaction, Zn, BrF2CCO2Et, aldehyde or ketone, one pot reaction. The yields for aldehyde was fine, but for ketone was poor. If CeCl3 was added, the yield for ketone improved to more than 60%. This was published in JFC.
About 7 year ago, an Amerian professor did the reaction, Zn, BrFHCCO2Et, aldehyde or ketone, one pot reaction, CeCl3 for Ketone yield was high. The result was published in JOC.
The conclusion: USA professors are much more easily get stuff published in high-quantity journals. 很好的东东！谢谢分享！ 分享一下，谢谢楼主 很不错的东东，谢谢啊 谢谢啦，我在硕士期间做过有机锌试剂，很感兴趣。 谢谢 不错
回复 10# yanhanice 的帖子
真是不错的东西页:
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