(E)-2,2,7,7-四甲基-2,7-二硅杂辛-4-烯 | 16054-35-6

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 中文名称: (E)-2,2,7,7-四甲基-2,7-二硅杂辛-4-烯
• 英文名称: (E)-1,4-bis(trimethylsilyl)but-2-ene
• 英文别名: 1,4-bis(trimethylsilyl)-2-butene；bis(trimetlysilyl)but-2-ene；trans-1.4-Bis-(trimethylsilyl)-buten-(2)；trimethyl-[(E)-4-trimethylsilylbut-2-enyl]silane
• CAS: 16054-35-6
• 化学式: C₁₀H₂₄Si₂
• 分子量: 200.472
• InChiKey: DHTZZPHEAHKIBY-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  (E)-2,2,7,7-四甲基-2,7-二硅杂辛-4-烯 在 硫酸 、 copper dichloride 作用下， 以 正戊烷 为溶剂， 反应 11.5h， 生成 [3-chloro-4-(phenylthio)butyl]trimethylsilane
  参考文献：
  名称：

  (E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

  摘要：

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.

  DOI：

  10.1021/jo970546c
• 作为产物：
  描述：

  六甲基二硅烷 、 cis-2-butene-1,4-diol bis-trifluoroacetate 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以50%的产率得到(E)-2,2,7,7-四甲基-2,7-二硅杂辛-4-烯
  参考文献：
  名称：

  Silylation of Allylic Trifluoroacetates and Acetates Using Organodisilanes Catalyzed by Palladium Complex

  摘要：

  Silylation of allylic acetates (1) using organodisilanes (2) was carried out in the presence of a catalytic amount of Pd(DBA)2-LiCl at 100 degrees C. The silylation proceeded smoothly without beta-hydrogen elimination of. resulting (pi-allyl)palladium intermediate. The added chloride salt such as LiCl or NaCl was indispensable for the catalytic activity. On the other hand, remarkable improvement of the silylation was realized by employing allylic trifluoroacetates (4) in place of the acetates (1) as the substrates. The silylation proceeded even at room temperature, and the added chloride salts was not necessary as the catalyst component. In the silylation, transmetalation of the disilanes (2) with (eta(3)-allyl)palladium intermediate (7) might be a critical step in the catalytic cycle. Model reactions for the transmetalation were carried out.

  DOI：

  10.1021/jo960345t

文献信息

• N-Heterocyclic Carbene Complexes Of Metal Imido Alkylidenes And Metal OXO Alkylidenes, And The Use Of Same
  申请人：UNIVERSITÄT STUTTGART

  公开号：US20170050994A1

  公开（公告）日：2017-02-23

  The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2′, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2′ stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1′ in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.

  该发明涉及一种N-杂环卡宾复合物，其一般公式为I至IV（I）（II）（III）（IV），其中A1代表NR2或PR2，A2代表CR2R2′，NR2，PR2，0或S，A3代表N或P，C代表卡宾碳原子，环B为未取代或单取代或多取代的5至7元环，取代基R2和R2′代表线性或支链的C1-Cw-烷基基团，如果N和N分别代表NR2或PR2，则它们可以相同也可以不同，公式I、II、III或IV中的M代表Cr、Mo或W，公式I至IV中的X1或X2是相同或不同的，代表C1-C1s羧酸盐和C1-C1s-烷氧基等，Y为氧或硫等，Z为线性或支链的C1-Cw-烷氧基基团等，公式I至IV中的R1和R1′为脂肪族或芳香族基团等。这些化合物特别适用作为烯烃重排反应的催化剂，并相比已知的Schrock卡宾复合物，具有明显增强的对官能团的耐受性，特别是对醛、二级胺、腈、羧酸和醇等的耐受性增强。
• HIGHLY Z-SELECTIVE OLEFINS METATHESIS
  申请人：Schrock Richard R.

  公开号：US20110077421A1

  公开（公告）日：2011-03-31

  The present invention relates generally to catalysts and processes for the Z-selective formation of internal olefin(s) from terminal olefin(s) via homo-metathesis reactions.

  本发明通常涉及催化剂和过程，用于通过同型交换反应从末端烯烃中Z-选择性地形成内部烯烃。
• Highly Z-selective olefins metathesis
  申请人：Massachusetts Institute of Technology

  公开号：US09079173B2

  公开（公告）日：2015-07-14

  The present invention relates generally to catalysts and processes for the Z-selective formation of internal olefin(s) from terminal olefin(s) via homo-metathesis reactions.

  本发明涉及催化剂和过程，用于通过同型烯烃交换反应从末端烯烃中Z-选择性地形成内部烯烃。
• Synthesis of<i>trans</i>-1,4-Bis[dimethylorganylsilyl]-2-butenes
  作者：Wolf Jürgen Richter、Brigitte Neugebauer

  DOI：10.1055/s-1985-31428

  日期：——

  The reaction of chlorodimethylorganosilanes [Cl-Si(CH3)2R; R = CH3. -CH=CH2, -CH2Cl, -CH2-CH=CH2. C6H5) with magnesiumbutadiene at 0°C in toluene gives trans-1,4-bis[dimethylorganylsilyl]-2-butenes in 55-88% yield. The amount of (Z)-isomer ranges from 0 to 17% depending on the organic substituent; no 1.2-disylilated products were detected.

  氯二甲基有机硅烷 [Cl-Si(CH3)2R; R = CH3, -CH=CH2, -CH2Cl, -CH2-CH=CH2, C6H5] 在0°C的托烯中与镁丁二烯发生反应，生成trans-1,4-双 [二甲基有机硅基]-2-丁烯，产率为55-88%。(Z)-异构体的含量范围为0到17%，具体取决于有机取代基；未检测到1,2-二硅基化产物。
• Cobalt-catalyzed mono-coupling of R 3 SiCH 2 MgCl with 1,2-dihalogenoethylene: a general route to γ-substituted ( E )-allylsilanes
  作者：Taku Kamachi、Akiko Kuno、Chikashi Matsuno、Sentaro Okamoto

  DOI：10.1016/j.tetlet.2004.04.098

  日期：2004.6

  um chloride (TMSCH2MgCl) with 1,2-dihalogenoethylene in the presence of 1 mol % of Co(II) or Co(III) acetylacetonate in THF or THF–NMP proceeded exclusively in a mono-coupling pathway to provide 3-trimethylsilyl-1-halogeno-1-propene with >99% of E geometry in high yield, which was converted to a variety of γ-substituted allylsilanes by Ni- or Pd-catalyzed coupling with organometallic compounds.

  三甲基甲硅烷基甲基氯化镁（TMSCH 2 MgCl）与1,2-二卤代乙烯在THF或THF-NMP中存在1 mol％的乙酰丙酮化Co（II）或Co（III）的反应仅通过单偶联途径进行具有> 99％E几何形状的3-三甲基甲硅烷基-1-卤代-1-丙烯，收率高，可通过Ni-或Pd催化与有机金属化合物的偶合反应转化为各种γ-取代的烯丙基硅烷。