Research News, May 26th, 2011
金属杂环试剂研究取得系列进展
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.
背景介绍：
金属有机化合物作为合成试剂广泛应用于合成化学有关的各个领域，一直受到学术界和工业界的极大关注。本小组十余年来在双金属有机合成试剂以及金属杂环试剂研究方面开展了工作。2010年，本组应邀在Acc. Chem. Res. 上系统总结了本实验室发现和发展的双（锂）金属有机试剂，详细阐述了双金属有机试剂的“协同效应”理念及其产生的新反应类型和合成化学新方法（Zhenfeng Xi,* 1,4-Dilithio-1,3-dienes: Reaction and Synthetic Applications, Acc. Chem. Res. 2010, 43, 1342-1451）。
最近，本组再次应邀在Acc. Chem. Res. 上系统总结了本实验室近十年来在金属杂环试剂研究方面的工作。该文详细阐述了金属有机活性中间体与底物间的“协同效应”，以及本实验室“基于机理研究和活性中间体的合成化学”研究理念。该系列工作研究发现，金属有机活性中间体在配体的配位作用下，可以发生多种意想不到的结构变化，类似于一个“化学变形金刚”(Chemical Transformer)，实现了金属有机活性中间体中化学键的选择性切断与重组，生成了其它方法不能合成的新型金属有机化合物以及结构多样的环状有机化合物。
本组发表的有关研究代表性原始论文如下：
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.