cis-1,1-dimethyl-2,5-diphenyl-1-silacyclopent-3-ene | 120881-25-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-1,1-dimethyl-2,5-diphenyl-1-silacyclopent-3-ene
• 英文别名: cis-1,1-Dimethyl-2,5-diphenylsilacyclopent-3-ene；cis-2,5-dihydro-1,1-dimethyl-2,5-diphenylsilole；(2S,5R)-1,1-dimethyl-2,5-diphenyl-2,5-dihydrosilole
• CAS: 120881-25-6
• 化学式: C₁₈H₂₀Si
• 分子量: 264.442
• InChiKey: YRZXTMMJKPLFDH-HDICACEKSA-N

物化性质

• 沸点：
  359.7±42.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  cis-1,1-dimethyl-2,5-diphenyl-1-silacyclopent-3-ene 在 C₁₀H₂Cl₂O₂ 作用下， 以 苯 为溶剂， 反应 12.0h， 以78%的产率得到1,1-dimethyl-2,5-diphenylsilole
  参考文献：
  名称：

  钯催化的亚甲硅烷-1,3-二烯 [4 + 1] 环加成反应，使用（氨基甲硅烷基）硼酸酯作为亚甲硅烷的合成等价物

  摘要：

  硅原子上带有二烷基氨基的甲硅烷基硼酸酯在钯催化剂的存在下与 1,3-二烯反应，通过有效地从甲硅烷基硼酸酯转移甲硅烷基，以高产率得到硅杂环戊 3-烯（即 2,5-二氢硅酮） 1,3-二烯的酯。[4 + 1] 环加成适用于母体 1,3-丁二烯和各种具有甲硅烷氧基、氰基和酯基团的单、二和三取代的 1,3-二烯。在与 5,7-十二二烯的任一立体异构体的反应中发生立体有择的环形成：(E,E)-二烯产生顺式产物，而在异构体 (E,Z) 的反应中观察到反式产物的选择性形成)-二烯。[4 + 1] 环加成，然后用 DDQ 或氯苯醌脱氢得到 2,4- 和 2,5- 二芳基甲硅烷。

  DOI：

  10.1021/ja907170p
• 作为产物：
  描述：

  1,4-二苯基-1,3丁二烯 、 二氯二甲基硅烷 在 lithium biphenylide 、 calcium iodide 作用下， 生成 cis-1,1-dimethyl-2,5-diphenyl-1-silacyclopent-3-ene
  参考文献：
  名称：

  Organocalcium chemistry: preparation and reactions of highly reactive calcium

  摘要：

  DOI：

  10.1021/jo00304a016

文献信息

• Borole derivatives XXI, 2,5-diphenyl-2,5,-dihydro-1H-boroles; strctures of tert-butyl-2,5,-diphenyl-2,5-dihydro-1H-borole and of bis(tmeda) lithium 2,5-diphenyl-2,5-dihydro-1H-borolediide
  作者：Gerhard E. Herberich、Trixie Wagner、Hans-W. Marx

  DOI：10.1016/0022-328x(95)05818-a

  日期：1995.10

  The magnesium reagent Mg(C(4)H(4)Ph(2))(THF)(3) derived from (E,E)-1,4-diphenyl-1,3-butadiene reacts with boron dihalides BCl2(NR(2)) (R=Me, Et,Pr-i) and (t)BuBF(2) to give 2,5-dihydro-2,5-diphenyl-1H-boroles 2,5-Ph(2)C(4)H(4)BNR(2) (la-lc) and 2,5-Ph(2)C(4)H(4)B(t)Bu (Id) as mixtures of cis-trans isomers. cis-ld possesses a classical structure with a ring folding of 8 degrees along the line C-2,C-5 of the C4B ring. The dimethylamino compounds la undergo metallation when treated with LDA in THF. After addition of TMEDA, the product can be crystallized from hexane-THF (2:1) as [Li(TMEDA)](2)[2,5-Ph(2)C(4)H(2)BNMe(2)] (3). The structure of 3 is that of a contact ion triple with a triple-decker-like arrangement of the borole ring and two [Li(TMEDA)](+) units.
• Organocalcium chemistry: preparation and reactions of highly reactive calcium
  作者：Tse Chong Wu、Heping Xiong、Reuben D. Rieke

  DOI：10.1021/jo00304a016

  日期：1990.8
• Facile formation of substituted 2-butene-1,4-diylmagnesium using highly reactive magnesium. A simple approach to complex carbocycles and functionalized ketones
  作者：Heping Xiong、Reuben D. Rieke

  DOI：10.1021/jo00275a001

  日期：1989.7
• Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles
  作者：Reuben D. Rieke、Heping Xiong

  DOI：10.1021/jo00009a034

  日期：1991.4

  Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.
• Palladium-Catalyzed Silylene-1,3-Diene [4 + 1] Cycloaddition with Use of (Aminosilyl)boronic Esters as Synthetic Equivalents of Silylene
  作者：Toshimichi Ohmura、Kohei Masuda、Ichiro Takase、Michinori Suginome

  DOI：10.1021/ja907170p

  日期：2009.11.25

  3-dienes having silyloxy, cyano, and ester groups. Stereospecific ring formation took place in the reaction with either stereoisomer of 5,7-dodecadiene: the (E,E)-diene gave the cis product, whereas selective formation of the trans product was observed in the reaction of the isomeric (E,Z)-diene. The [4 + 1] cycloaddition followed by dehydrogenation with DDQ or chloranil afforded 2,4- and 2,5-diarylsiloles

  硅原子上带有二烷基氨基的甲硅烷基硼酸酯在钯催化剂的存在下与 1,3-二烯反应，通过有效地从甲硅烷基硼酸酯转移甲硅烷基，以高产率得到硅杂环戊 3-烯（即 2,5-二氢硅酮） 1,3-二烯的酯。[4 + 1] 环加成适用于母体 1,3-丁二烯和各种具有甲硅烷氧基、氰基和酯基团的单、二和三取代的 1,3-二烯。在与 5,7-十二二烯的任一立体异构体的反应中发生立体有择的环形成：(E,E)-二烯产生顺式产物，而在异构体 (E,Z) 的反应中观察到反式产物的选择性形成)-二烯。[4 + 1] 环加成，然后用 DDQ 或氯苯醌脱氢得到 2,4- 和 2,5- 二芳基甲硅烷。