硅烷,(1,1-二甲基乙基)二甲基(三苯基甲锡烷基)- | 185962-47-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 硅烷,(1,1-二甲基乙基)二甲基(三苯基甲锡烷基)-
• 英文名称: tert-butyldimethylsilyl triphenylstannane
• 英文别名: Me2ButSiSnPh3；tBuMe2SiSnPh3
• CAS: 185962-47-4
• 化学式: C₂₄H₃₀SiSn
• 分子量: 465.298
• InChiKey: PHRLMBPBVOUZJM-UHFFFAOYSA-N

物化性质

• 沸点：
  439.2±18.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  N-(buta-2,3-dien-1-yl)-4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide 、 硅烷,(1,1-二甲基乙基)二甲基(三苯基甲锡烷基)- 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三(五氟苯基)膦 作用下， 以 氘代苯 为溶剂， 以41%的产率得到
  参考文献：
  名称：

  双官能化环化中的区域和立体化学控制：丙二炔前体在碳环和杂环合成中的应用。

  摘要：

  DOI：

  10.1021/ja011281t
• 作为产物：
  描述：

  三苯基氢化锡 、 叔丁基二甲基氯硅烷 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 以99%的产率得到硅烷,(1,1-二甲基乙基)二甲基(三苯基甲锡烷基)-
  参考文献：
  名称：

  Axial Chirality in 1,4-Disubstituted (ZZ)-1,3-Dienes. Surprisingly Low Energies of Activation for the Enantiomerization in Synthetically Useful Fluxional Molecules

  摘要：

  Trialkylsilyltrialkylstannes (R3Si-SnR'(3)) add to 1,6-diynes in the presence of Pd(0) and trispentaflurophenylphosphine to give 1,2-dialkylidenecyclopentanes with terminal silicon and tin substituents. The (ZZ)-geometry of these s-cis-1,3-dienes, resulting from the organometallic reaction mechanisms involved, forces the silicon and tin groups to be nonplanar, thus making the molecules axially chiral. There is rapid equilibration between the two helical forms at room-temperature irrespective of the size of the Si and Sn substituents. However, the two forms can be observed by H-1, C-13, and Sn-119 NMR spectroscopy at low temperature. The rates of enantiomerization, which depend on the Si and Sn substituents, and the substitution pattern of the cylopentane ring can be studied by dynamic NMR spectroscopy using line shape analysis. The surprisingly low energies of activation (DeltaG(double dagger) = 52-57 kJ mol(-1)) for even the bulky Si and Sn derivatives may be attributed to a widening of the exo-cyclic bond-angles of the diene carbons.

  DOI：

  10.1021/ja035136m

文献信息

• Silylstannylation of Allenes and Silylstannylation−Cyclization of Allenynes. Synthesis of Highly Functionalized Allylstannanes and Carbocyclic and Heterocyclic Compounds
  作者：Ramaiah Kumareswaran、Seunghoon Shin、Isabelle Gallou、T. V. RajanBabu

  DOI：10.1021/jo049010z

  日期：2004.10.1

  silicon−tin reagents to undergo the cyclization illustrate the scope and limitations of the reaction. Based on the isolation of intermediates, a mechanism for the formation of the cyclic compounds is proposed. Model transition states to explain the stereoselectivity in cyclization of substituted allenynes are provided. Further elaboration using the vinyltin and vinylsilane moieties should lead to highly functionalized

  通过Pd催化（0），trialkylsilyltrialkylstannane（R 3 Si的SNR” 3）的试剂进行高度选择性添加到1,2-二烯-7-炔和1,2-二烯8 -炔，得到2- vinylalkylidenecyclopentanes有硅和双键上的锡取代基。二萘烷和硼烷锡的类似添加表明，与甲硅烷基锡的反应在处理双功能试剂的容易性和反应后产物的分离方面是优异的。化学和区域选择性由丙二烯单元增强的反应性控制，而（Z环苯乙烯基亚乙烯基的-（-）-几何形状是顺式碳共金属化和随后从Pd上的还原消除，并保留了乙烯基碳上的构型的结果。高度官能化的吡咯烷和吲哚唑烷的合成以及某些类型的烯丙炔和硅锡试剂不愿进行环化反应说明了反应的范围和局限性。基于中间体的分离，提出了形成环状化合物的机理。提供了模型过渡态以解释取代的烯丙炔环化中的立体选择性。使用乙烯基锡和乙烯基硅烷部分的进一步加工将导致高度官能化的
• Stereoselective Cyclization of Functionalized 1,<i>n</i>-Diynes Mediated by [X−Y] Reagents [X−Y = R₃Si−SnR′₃ or (R₂N)₂B−SnR′₃]: Synthesis and Properties of Atropisomeric 1,3-Dienes
  作者：Ramakrishna Reddy Singidi、Amanda M. Kutney、Judith C. Gallucci、T. V. RajanBabu

  DOI：10.1021/ja105939v

  日期：2010.9.22

  The borylstannane [-N(Me)CH2CH2(Me)N-]B-SnMe3 is a superior reagent capable of effecting bisfunctionalization-cyclization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dipropargylbenzenes, 2,2'-dipropargylbiphenyls, 4,5-dipropargyldioxolanes, and 1,4-dipropargyl-beta -lactams) where the more well-known silylstannanes fail. Variable-temperature NMR studies showed that conformational restraints imposed by selected backbones increase the activation barrier for the helical isomerization in (Z,2)-dienes that are generated in the cyclization of the diynes. In the biphenyl and dioxolane systems, the reactions proceed with surprisingly good regio- and stereoselectivity. The resulting diazaborolidine derivatives are hydrolytically unstable but can be isolated by recrystallization or precipitation. For further synthetic applications, it is advantageous to convert these compounds in situ into the corresponding dioxaborolidines with either retention of the Me3Sn group or replacement of this group via halodestannylation. The configurations of the vinyl moieties are preserved in these reactions. Highly functionalized dibenzocyclooctadienes, which adorn the carbon frames of several important cytotoxic natural products, can be synthesized using this chemistry.