Research News, Nov 24th, 2009
研究室工作进展 Nov. 24, 2009
引言：硅杂环化合物在有机硅化学中是一类重要的小分子环系化合物，广泛应用于有机化学, 金属有机化学以及材料化学等领域。结合本研究室的工作进展以及相关他人文献，我们就硅杂四元环化合物的合成和反应，硅杂六元环化合物的合成，以及硅杂六元环化合物的反应撰写了三篇中文综述，希望对从事有关领域的研究者有益。
Introduction: Silacycles are a class of important cyclic compounds in organosilicon chemistry, which have many applications in organic chemsitry, organometallic chemistry, polymer chemistry, and materials chemistry. Based on our research progress and others’ related work, we have published three review articles in Chinese on Synthesis and Reactivity of Four-membered Silacycles, Synthesis of Six-membered Silacycles, and Reactivity of Six-membered Silacycles.
硅杂四元环化合物的合成和反应
刘俊辉 张文雄 席振峰*
有机化学2009，29，491-503
硅杂四元环化合物在有机硅化学中是一类非常重要的小分子环系化合物, 广泛应用于有机化学, 金属有机化学以及材料化学。 环上只含有一个硅原子的硅杂环丁烷可以通过γ-卤代丙基硅烷的Grignard反应, Si=C键与烯烃的[2+2]环加成反应以及硅杂环丙烷的扩环反应合成; 环上只含有一个硅原子的硅杂环丁烯可以通过格式试剂或锂试剂参与的Si-C键的关环反应, 硅杂环丁烷的转化反应, 硅卡宾对C-H键的插入反应, Si=C键与炔烃的[2+2]环加成反应以及二炔基硅烷的分子内成环反应等途径合成。硅杂环丁烷和硅杂环丁烯由于存在环张力和具有一定的Lewis酸性, 能够通过扩环反应生成五元和六元含硅杂环化合物, 也能够通过开环反应生成不同结构的有机硅分子和聚合物, 抑或实现有机反应在温和条件下的转化。
Synthesis and Reactivity of Four-membered Silacycles
Junhui Liu, Wen-Xiong Zhang, and Zhenfeng Xi*
Chinese J. Org. Chem. (in Chinese) 2009, 29, 491-503
Four-membered silacycles are a class of important small cyclic compounds in organosilicon chemistry, which also have many applications to organic, organometallic, and polymer chemistry. Silacyclobutanes with one silicon atom in the ring can be synthesized by the Grignard reaction of γ-halopropylsilanes, cycloaddition of Si=C bond containing species with alkenes and ring expansion of silacyclopropanes. Silacyclobutenes with one silicon atom in the ring can be synthesized by Si-C bond forming ring-closure mediated by organolithium or Grignard reagents, conversion of silacyclobutanes, insertion of silylene into C-H bond, cycloaddition of Si=C bond containing species with alkynes, and intramolecular cyclization of bis(alkynyl)silanes. Due to the ring strain and Lewis acid character, silacyclobutanes and silacyclobutenes can undergo ring expansion reactions to afford five- and six-membered silacycles, or ring opening to give organosilicon molecules and materials as well as fulfill organic transformations under very mild conditions.
硅杂六元环化合物的合成
刘俊辉 张韶光 张文雄 席振峰*
化学进展 2009，12，1475-1486
硅杂六元环化合物在有机硅化学中是一类重要的小分子环系化合物,广泛应用于有机化学, 金属有机化学以及材料化学等领域。 环上只含有一个硅原子的硅杂六元环化合物具有多种合成方法: α, ω-双金属试剂的关环反应、硅烯参与的[4+2]环加成反应、C-Si键生成的关环反应、C-C键生成的关环反应、硅杂环的扩环反应。
Synthesis of Six-membered Silacycles
Junhui Liu, Shaoguang Zhang, Wen-Xiong Zhang, and Zhenfeng Xi*
Progress in Chemistry (in Chinese) 2009, 12, 1475-1486
Six-membered silacycles are a class of important cyclic compounds in organosilicon chemistry, which have many applications in organic, organometallic, and polymer chemistry. Six-membered silacycles with one silicon atom in the ring can be synthesized by the following methods: ring closure by silylation of α, ω-dimetallic compounds, [4+2] cycloaddition reaction involving silenes, ring closure by C-Si bond formation, ring closure by C-C bond formation, ring expansion reaction of smaller silacycles, and etc.
硅杂六元环化合物的反应
张韶光 刘俊辉 张文雄 席振峰*
化学进展 2009，12，1487-1493
硅杂六元环化合物在有机硅化学中是一类重要的小分子环系化合物, 广泛应用于有机化学, 金属有机化学以及材料化学等领域。环上只含有一个硅原子的硅杂六元环化合物的反应主要分为环外硅原子上的反应、立体选择性合成、硅原子α-位碳原子上的反应、插入反应、环加成反应、Si-C键的切断反应、硅杂苯衍生物合成以及金属配位反应等。
Reactivity of Six-membered Silacycles
Shaoguang Zhang, Junhui Liu, Wen-Xiong Zhang, Zhenfeng Xi*
Progress in Chemistry (in Chinese) 2009, 12, 1487-1493
Six-membered silacycles are a class of important cyclic compounds in organosilicon chemistry, which have many applications in organic, organometallic, and polymer chemistry. Eight kinds of reactions of six-membered silacycles with one silicon atom in the ring are mainly included. They are exocyclic reactions at the silicon atom, stereoselective organic transformations, reactions at the α-position of silicon atom, insertion reactions, cycloadditions, Si-C bond cleavage reactions, silabenzene derivatives formations and metal coordination reactions.