(Z)-2-Butenylchlorodimethylsilane | 73537-46-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z)-2-Butenylchlorodimethylsilane
• 英文别名: (Z)-2-butenyldimethylchlorosilane；but-2-en-1-ylchlorodimethylsilane；(Z)-chloro(crotyl)dimethylsilane；(Z)-Crotyldimethylchlorosilane；dimethyl((Z)-but-2-enyl)chlorosilane；[(Z)-but-2-enyl]-chloro-dimethylsilane
• CAS: 73537-46-9
• 化学式: C₆H₁₃ClSi
• 分子量: 148.708
• InChiKey: ZIIOFRVBHAVTFG-PLNGDYQASA-N

物化性质

• 沸点：
  60-65 °C(Press: 50 Torr)
• 密度：
  0.883±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (Z)-2-Butenylchlorodimethylsilane 在 lithium 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 o-((Z)-crotyldimethylsilyl)benzyl alcohol
  参考文献：
  名称：

  Intramolecular nucleophilic attack at silicon in o-silylbenzyl alcohols. Generation of allyl and benzyl anion equivalents

  摘要：

  Substituted silyl ethers of o-bromobenzyl alcohols and the derived o-silylbenzyl alcohols were used to transfer allyl and benzyl groups from silicon to the electrophiles benzaldehyde and benzophenone in excellent yields. gamma-Oxidosilane intermediates (and possibly hypercoordinated silicon intermediates) are postulated. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.09.127
• 作为产物：
  描述：

  (Z)-crotyltrichlorosilane 、 甲基锂 以 乙醚 为溶剂， 反应 16.0h， 生成 (Z)-2-Butenylchlorodimethylsilane
  参考文献：
  名称：

  通过硅酸双胍离子对对酰基硅烷进行对映选择性 1,2-阴离子重排

  摘要：

  报道了高度对映选择性双胍催化的酰基硅烷串联重排。通过在硅上添加氟化物来活化酰基硅烷以形成五配位阴离子硅酸盐中间体。然后硅酸盐经历烷基或芳基从硅原子迁移到相邻的羰基碳原子（1,2-阴离子重排），然后进行 [1,2]-布鲁克重排，以高产率提供具有优异对映选择性的仲醇（高达 95% ee）。α-甲硅烷基甲醇中间体的分离以及 DFT 计算表明，1,2-阴离子重排是通过双胍硅酸盐离子对发生的，这是立体确定步骤。然后通过随后的 [1,2]-布鲁克重排保留形成的手性中心而不发生反转。巴豆酰基硅烷顺利转化为高烯丙基线性巴豆醇，保留 E/Z 几何结构，未检测到支链醇。这清楚地表明 1,2-阴离子重排是通过三元而不是五元过渡态发生的。

  DOI：

  10.1021/jacs.7b13056

文献信息

• A new synthesis of 1,3-dihydrobenzo[1,2]oxasiloles by a novel rearrangement of a pentavalent silicon intermediate
  作者：George Bashiardes、Vanessa Chaussebourg、G�raldine Laverdan、Jacques Pornet

  DOI：10.1039/b311804e

  日期：——

  A new synthesis of benzo[1,2]oxasiloles is described, wherein an unprecedented intramolecular allylic transposition takes place probably involving a pentavalent silicon intermediate.

  描述了一种新的苯并[1,2]恶唑的合成方法，其中发生了前所未有的分子内烯丙基转移，可能涉及五价硅中间体。
• Gold-catalysed intramolecular trans-allylsilylation of alkynes forming 3-allyl-1-silaindenes
  作者：Takanori Matsuda、Sho Kadowaki、Yoshiyuki Yamaguchi、Masahiro Murakami

  DOI：10.1039/b804721a

  日期：——

  3-Allyl-1-silaindenes are synthesised from alkynes having an allylsilane moiety by a gold-catalysed intramolecular trans-allylsilylation reaction.

  3-烯丙基-1-硅杂蒽是通过金催化的分子内反烯丙基硅烷化反应，从具有烯丙基硅烷分子的炔烃中合成的。
• Alkenylsilylazetidinone intermediates for carbapenems
  申请人：Shionogi & Co., Ltd.

  公开号：US04960880A1

  公开（公告）日：1990-10-02

  An intermediate for synthesizing carbapenems is produced through (1) a reaction of 4-(leaving group substituted)-2-azetidinone (I) with (alk-2-enyl)halosilane (II) to afford 4-(leaving group substituted)-1-(alk-2-enyl)silyl-2-azetidinone (III) and then (2) a reaction of the product 4-(leaving group substituted)-1-alk-2-enyl)silyl-2-azetidinone (III) with acid to give the corresponding 4-(alk-2-enyl)-2-azetidinone (IV). ##STR1## (The symbols are defined in the specification)

  合成碳青霉烯的中间体是通过以下步骤制备的：(1)将4-(含有离去基取代)-2-氮杂环己酮(I)与(烷基-2-烯基)卤代硅烷(II)反应，得到4-(含有离去基取代)-1-(烷基-2-烯基)硅基-2-氮杂环己酮(III)，然后(2)将产物4-(含有离去基取代)-1-烷基-2-烯基)硅基-2-氮杂环己酮(III)与酸反应，得到相应的4-(烷基-2-烯基)-2-氮杂环己酮(IV)。##STR1## (符号在说明书中定义)
• Fuerstner, Alois; Voigtlaender, David, Synthesis, 2000, # 7, p. 959 - 969
  作者：Fuerstner, Alois、Voigtlaender, David

  DOI：——

  日期：——
• Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts
  作者：Scott E. Denmark、Nathan S. Werner

  DOI：10.1021/ja805951j

  日期：2008.12.3

  The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 degrees C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (2)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.