Research News, Nov 24th, 2009
研究室工作進展 Nov. 24, 2009
引言：矽雜環化合物在有機矽化學中是一類重要的小分子環系化合物，廣泛應用于有機化學, 金屬有機化學以及材料化學等領域。結合本研究室的工作進展以及相關他人文獻，我們就矽雜四元環化合物的合成和反應，矽雜六元環化合物的合成，以及矽雜六元環化合物的反應撰寫了三篇中文綜述，希望對從事有關領域的研究者有益。
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.
矽雜四元環化合物的合成和反應
劉俊輝 張文雄 席振峰*
有機化學2009，29，491-503
矽雜四元環化合物在有機矽化學中是一類非常重要的小分子環系化合物, 廣泛應用于有機化學, 金屬有機化學以及材料化學。 環上隻含有一個矽原子的矽雜環丁烷可以通過γ-鹵代丙基矽烷的Grignard反應, Si=C鍵與烯烴的[2+2]環加成反應以及矽雜環丙烷的擴環反應合成; 環上隻含有一個矽原子的矽雜環丁烯可以通過格式試劑或锂試劑參與的Si-C鍵的關環反應, 矽雜環丁烷的轉化反應, 矽卡賓對C-H鍵的插入反應, Si=C鍵與炔烴的[2+2]環加成反應以及二炔基矽烷的分子内成環反應等途徑合成。矽雜環丁烷和矽雜環丁烯由于存在環張力和具有一定的Lewis酸性, 能夠通過擴環反應生成五元和六元含矽雜環化合物, 也能夠通過開環反應生成不同結構的有機矽分子和聚合物, 抑或實現有機反應在溫和條件下的轉化。
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.
矽雜六元環化合物的合成
劉俊輝 張韶光 張文雄 席振峰*
化學進展 2009，12，1475-1486
矽雜六元環化合物在有機矽化學中是一類重要的小分子環系化合物,廣泛應用于有機化學, 金屬有機化學以及材料化學等領域。 環上隻含有一個矽原子的矽雜六元環化合物具有多種合成方法: α, ω-雙金屬試劑的關環反應、矽烯參與的[4+2]環加成反應、C-Si鍵生成的關環反應、C-C鍵生成的關環反應、矽雜環的擴環反應。
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.
矽雜六元環化合物的反應
張韶光 劉俊輝 張文雄 席振峰*
化學進展 2009，12，1487-1493
矽雜六元環化合物在有機矽化學中是一類重要的小分子環系化合物, 廣泛應用于有機化學, 金屬有機化學以及材料化學等領域。環上隻含有一個矽原子的矽雜六元環化合物的反應主要分為環外矽原子上的反應、立體選擇性合成、矽原子α-位碳原子上的反應、插入反應、環加成反應、Si-C鍵的切斷反應、矽雜苯衍生物合成以及金屬配位反應等。
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.