Research News, May 26th, 2011
金屬雜環試劑研究取得系列進展
Zirconocene and Si-tethered Diynes: A Happy Match Directed towards Organometallic Chemistry and Organic Synthesis
Wen-Xiong Zhang, Shaoguang Zhang, and Zhenfeng Xi*
Acc. Chem. Res. 2011, ASAP 20110525,DOI: 10.1021/ar200078e
Characterizing reactive organometallic intermediates is critical for understanding the mechanistic aspects of metal-mediated organic reactions. Moreover, the isolation of reactive organometallic intermediates can often result in the ability to design new synthetic methods. In this Account, we outline synthetic methods that we developed for a variety of diverse Zr/Si organo-bi-metallic compounds and Si/N heteroatom- organic compounds through the detailed study of zircona cyclobutene–silacyclobutene fused compounds.
Our results show that the zirconocene and the Si-tethered diyne cooperate as a “chemical transformer” after treatment with various substrates, leading to a diverse range of cyclic Zr/Si organo-bi-metallic compounds. This mechanism-derived synthesis of organometallic and organic compounds demonstrates that the investigation of metal-mediated reactions and the isolation of reactive organometallic intermediates not only contribute to the understanding of complex reactions, but can also lead to the discovery of synthetically useful methods.
背景介紹：
金屬有機化合物作為合成試劑廣泛應用于合成化學有關的各個領域，一直受到學術界和工業界的極大關注。本小組十餘年來在雙金屬有機合成試劑以及金屬雜環試劑研究方面開展了工作。2010年，本組應邀在Acc. Chem. Res. 上系統總結了本實驗室發現和發展的雙（锂）金屬有機試劑，詳細闡述了雙金屬有機試劑的“協同效應”理念及其産生的新反應類型和合成化學新方法（Zhenfeng Xi,* 1,4-Dilithio-1,3-dienes: Reaction and Synthetic Applications, Acc. Chem. Res. 2010, 43, 1342-1451）。
最近，本組再次應邀在Acc. Chem. Res. 上系統總結了本實驗室近十年來在金屬雜環試劑研究方面的工作。該文詳細闡述了金屬有機活性中間體與底物間的“協同效應”，以及本實驗室“基于機理研究和活性中間體的合成化學”研究理念。該系列工作研究發現，金屬有機活性中間體在配體的配位作用下，可以發生多種意想不到的結構變化，類似于一個“化學變形金剛”(Chemical Transformer)，實現了金屬有機活性中間體中化學鍵的選擇性切斷與重組，生成了其它方法不能合成的新型金屬有機化合物以及結構多樣的環狀有機化合物。
本組發表的有關研究代表性原始論文如下：
1 Xiaohua Sun, Congyang Wang, Zhiping Li, Shiwei Zhang, and Zhenfeng Xi,*
J. Am. Chem. Soc. 2004, 126, 7172-7173.
2 Tao Yu, Xiaohua Sun, Congyang Wang, Liang Deng, and Zhenfeng Xi,*
Chem. Eur. J. 2005, 11, 1895-1902.
3 Junhui Liu, Xiaohua Sun,Mikihiro Miyazaki, Lantao Liu, Congyang Wang, and Zhenfeng Xi,*
J. Org. Chem. 2007, 72, 3137-3140.
4 Junhui Liu, Shaoguang Zhang, Wenxiong Zhang, and Zhenfeng Xi*
Organometallics 2009, 28, 413-417.
5 Wen-Xiong Zhang, Shaoguang Zhang, Xiaohua Sun, Masayoshi Nishiura, Zhaomin Hou,* and Zhenfeng Xi*
Angew. Chem. Int. Ed. 2009, 48, 7227-7231.
6 Shaoguang Zhang, Xiaohua Sun, Wen-Xiong Zhang, and Zhenfeng Xi*
Chem. Eur. J. 2009, 15, 12608 – 12617.
7 Qian Luo, Chao Wang, Li Gu, Wen-Xiong Zhang and Zhenfeng Xi*
Chem. Asian J. 2010, 5, 1120-1128.
8 Shaoguang Zhang, Wen-Xiong Zhang, and Zhenfeng Xi*
Chem. Eur. J. 2010, 16, 8419-8426.
9 Shaoguang Zhang, Wen-xiong Zhang, Jin Zhao, and Zhenfeng Xi,*
J. Am. Chem. Soc. 2010, 132, 14042-14045.
10 Shaoguang Zhang, Wen-Xiong Zhang, Jing Zhao, and Zhenfeng Xi*
Chem. Eur. J. 2011, 17, 2442-2449.
11 Shaoguang Zhang, Jing Zhao, Wen-Xiong Zhang, and Zhenfeng Xi*
Org. Lett. 2011, 13, 1626-1629.