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Mechanistic Insight into the Copper-Catalyzed Phosphorylation of Terminal Alkynes: A Combined Theoretical and Experimental Study

2014-7-13 09:21| 发布者: Mcdull| 查看: 2374| 评论: 0|原作者: chemliu66|来自: 捷报频传

摘要: 三月二十七号投稿,先后经历两次小改,七月一号接收。 这篇论文的idea起始于去年在八月在姐姐家休息的时候,无意中看到一篇chem comm计算Cu/O2体系炔烃和-CF3氧化偶联的计算。想起组里09年发的一篇jacs可能会有相 ...
Article

Mechanistic Insight into the Copper-Catalyzed Phosphorylation of Terminal Alkynes: A Combined Theoretical and Experimental Study

Liu Liu †||, Yile Wu †, Zeshu Wang ‡, Jun Zhu *‡, and Yufen Zhao *†§
† Key Laboratory for Chemical Biology of Fujian Province, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
‡ State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
§ Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China
|| Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0343, United States
J. Org. Chem., Article ASAP
DOI: 10.1021/jo5007174
Publication Date (Web): July 1, 2014
Copyright © 2014 American Chemical Society
*E-mail: jun.zhu@xmu.edu.cn. Web: http://junzhu.chem8.org., *E-mail: yfzhao@xmu.edu.cn. Web: http://chem.xmu.edu.cn/group/yfzhao/zhao-home.html.

Abstract
jo-2014-007174_0009.gif
The reaction mechanism of copper-catalyzed phosphorylation of terminal alkynes under different conditions has been investigated experimentally and theoretically. The important role of dioxygen has been elucidated, including the formation of η1-superoxocopper(II), η2-superoxocopper(III), μ-η2:η2-peroxodicopper(II), and bis(μ-oxo)dicopper(III) complexes. More importantly, the proton transfer from the dialkyl phosphonate (in the form of phosphite) to the bridging oxygen atom entails the migration of the deprotonated phosphonate to the terminal alkyne, leading to the formation of a C–P bond with an activation barrier of only 1.8 kcal/mol. In addition, a particularly stable six-centered dicopper(I) species is formed with the migration of both of the Ph2P(O) groups from the copper atoms to the oxygen atoms of the bis(μ-oxo) bridge, explaining the experimental observation that secondary phosphine oxides can be oxidized to the phosphinic acids. Thus, the diphenylphosphine oxide was added to the reaction mixture dropwise to minimize the concentration during the reaction course. Gratifyingly, the coupling product was generated almost quantitatively when the reaction was completed.

三月二十七号投稿,先后经历两次小改,七月一号接收。

这篇论文的idea起始于去年在八月在姐姐家休息的时候,无意中看到一篇chem comm计算Cu/O2体系炔烃和-CF3氧化偶联的计算。想起组里09年发的一篇jacs可能会有相似的机理。所以尝试了画了一下机理图。发现可以尝试做计算。于是花了大概两个多月来做计算。期间发现有一个过渡态,基组用6-31G(d)总是找不到,所以尝试了其他基组可以找到,于是又用D95v(d)把体系重新run了一遍。

在计算的时候看到Jingquan Yu做的一篇C-H活化生成C-P键的jacs,其提到磷试剂很容易和催化剂结合在一起,使其失效。避免的方法就是滴加磷试剂。于是在去年九月去厦大办手续的时候,尝试滴加二苯基磷氧在体系中,发现crude product几乎是定量转化。但是由于自己时间有限,就让组里的人帮忙尝试扩展一些底物。

可惜这个方法对其他的炔,尤其是脂肪族的炔烃,转化率非常低。所以就放弃了扩展底物,以主打机理为主。

总体还是比较顺,四个审稿人,一个大改,一个直接接收,一个据搞(没提什么问题),一个小改。

总体自己发了八篇论文,还是最喜欢这篇论文的。

最后附上论文链接:

http://pubs.acs.org/doi/abs/10.1021/jo5007174

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