1-<(trimethylsilyl)oxy>-1-ethoxy-1,3-butadiene | 114996-00-8

• 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: 1-<(trimethylsilyl)oxy>-1-ethoxy-1,3-butadiene
• 英文别名: (Z)-1-ethoxy-1-(trimethylsiloxy)-1,3-butadiene；(1Z)-(1-ethoxy-buta-1,3-dienyloxy)-trimethyl silane；[(1Z)-1-ethoxybuta-1,3-dienoxy]-trimethylsilane
• CAS: 114996-00-8
• 化学式: C₉H₁₈O₂Si
• 分子量: 186.326
• InChiKey: GIJZHQCVBVIUEL-HJWRWDBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-<(trimethylsilyl)oxy>-1-ethoxy-1,3-butadiene 在 氟化氢吡啶 、 亚硝基苯 作用下， 以 二氯甲烷 为溶剂， 反应 50.0h， 以39%的产率得到乙基(2E)-4-羟基-2-丁烯酸酯
  参考文献：
  名称：

  γ-Oxygenation of α,β-Unsaturated Esters by Vinylogous O-Nitroso Mukaiyama Aldol Reaction

  摘要：

  A practical procedure has been developed for gamma-oxygenation of alpha,beta-unsaturated esters by a vinylogous O-nitroso Mukaiyama aldol reaction followed by a one-pot N-O bond heterolysis of the in situ generated gamma-aminoxy-alpha,beta-unsaturated esters.

  DOI：

  10.1021/ol1021433
• 作为产物：
  描述：

  三甲基氯硅烷 、 反式-2-丁烯酸乙酯 在 六甲基磷酰三胺 、 lithium diisopropyl amide 作用下， 生成 1-<(trimethylsilyl)oxy>-1-ethoxy-1,3-butadiene
  参考文献：
  名称：

  Regiochemical control in the preparation of 2-(nosyloxy) .beta.,.gamma.-unsaturated esters and 4-(nosyloxy) .alpha.,.beta.-unsaturated esters from 1-[(trimethylsilyl)oxy]-1-alkoxy 1,3-dienes

  摘要：

  A series of 1-[(trialkylsilyl)oxy]-1-alkoxy 1,3-dienes 1a-i were found to react with p-nitrobenzenesulfonyl peroxide in the presence of sodium methoxide or zinc chloride to give alkyl 2-[[(p-nitrophenyl)sulfonyl]oxy] beta-gamma-unsaturated esters 3 and alkyl 4-[[(p-nitrophenyl)sulfonyl]oxy] alpha,beta-unsaturated esters 4 which are readily separable. The regioselectivity is determined by kinetic versus thermodynamic control. When positions 2 or 4 of the diene are unsubstituted, the 2-isomer is the major product and is the kinetically fastest formed product. It can be thermally rearranged to the more stable 4-isomer. When alkyl substituents are present at either the 2- or 4-positions, only the 4-isomer is obtained. Substitution for nosylate by amine nucleophiles occurs by an S(N)2 process. Thus 2-amino beta,gamma-unsaturated esters and 4-amino alpha,beta-unsaturated esters can be prepared from the appropriate starting nosylate.

  DOI：

  10.1021/jo00003a022

文献信息

• Catalytic and Asymmetric Vinylogous Mukaiyama Reactions on Aliphatic Ketones:  Formal Asymmetric Synthesis of Taurospongin A
  作者：Xavier Moreau、Belen Bazán-Tejeda、Jean-Marc Campagne

  DOI：10.1021/ja051573k

  日期：2005.5.25

  Catalytic asymmetric vinylogous Mukaiyama reactions on ketones, leading to the formation of alpha,beta-unsaturated lactones with tertiary alcohols, have been described (11 examples, up to 93% ee). This methodology has been applied in a formal enantioselective synthesis of taurospongin A (12 steps, 6% overall yield).

  已经描述了酮上的催化不对称乙烯基 Mukaiyama 反应，导致与叔醇形成 α,β-不饱和内酯（11 个例子，高达 93% ee）。该方法已应用于正式对映选择性合成 taurospongin A（12 步，总产率 6%）。
• Sulfoximines as Ligands in Copper-Catalyzed Asymmetric Vinylogous Mukaiyama-Type Aldol Reactions
  作者：Pauline Rémy、Martin Langner、Carsten Bolm

  DOI：10.1021/ol060077d

  日期：2006.3.1

  [reaction: see text] gamma,delta-Unsaturated alpha-hydroxy diesters with quaternary centers have been obtained with up to 99% ee in high yields using catalysts prepared from copper(II) triflate and C(1)-symmetric aminosulfoximines.

  [反应：见正文]使用由三氟甲磺酸铜（II）和C（1）对称的氨基亚砜肟基制备的催化剂，可以以高达99％ee的高收率获得具有季中心的γ，δ-不饱和α-羟基二酯。
• Mechanism of Enolate Transfer between Si and Cu
  作者：Samira Bouaouli、Kim Spielmann、Emmanuel Vrancken、Jean-Marc Campagne、Hélène Gérard

  DOI：10.1002/chem.201800099

  日期：2018.5.2

  OMe) and a substituted enolate chain between SiMe3 and various CuI complexes was examined. Reaction mechanisms pass through a cyclic transition state in which the reaction coordinate is associated with rotation of the SiMe3 moiety. The dependence of the thermodynamic and kinetic features on the nature of the active and ancillary ligands was examined. Formation of copper enolate is shown to be favored

  考察了SiMe 3和各种Cu I络合物之间X（F，Cl，OMe）和取代的烯醇酸酯链的交换。反应机理通过循环过渡状态，其中反应坐标与SiMe 3部分的旋转相关。检查了热力学和动力学特征对活性和辅助配体性质的依赖性。当使用稳定的烯醇化物时，表明烯醇铜的形成是有利的。用Cl代替F可逆转反应的优先选择。与其他Si-X键相比，这与Cu-Cl和Si-Cl键能之间的微小差异有关，后者系统地比它们的Cu-X类似物强。
• Intertwined Analytical, Experimental and Theoretical Studies on the Formation and Structure of a Copper Dienolate
  作者：Baptiste Lecachey、Laetitia Palais、Benoît Courcy、Samira Bouauli、Muriel Durandetti、Hassan Oulyadi、Anne Harisson‐Marchand、Jacques Maddaluno、Hélène Gérard、Emmanuel Vrancken、Jean‐Marc Campagne

  DOI：10.1002/chem.202100596

  日期：2021.5.20

  a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate

  讨论了甲硅烷基二烯酸酯，Cu（II）盐和TBAT的反应产生相应的二烯丙基铜的反应。NMR和循环伏安分析相结合，首先突出了TBAT在Cu（II）还原为Cu（I）和预催化物质结构中的作用。从这些第一结果中，第二组NMR和理论研究使得能够确定二烯酸铜铜催化物质的结构和形成机理。最后，我们表明，铜催化剂通过二烯醇铜中间体促进了甲硅烷基二烯醇盐前体的E / Z s-顺式/ s-反式平衡。所有这些结果揭示了催化的和不对称的乙烯基Mukaiyama反应的某些特性。
• Stereospecific Hydrogenolysis of Lactones: Application to the Total Syntheses of (<i>R</i>)-<i>ar</i>-Himachalene and (<i>R</i>)-Curcumene
  作者：Kim Spielmann、Renata Marcia de Figueiredo、Jean-Marc Campagne

  DOI：10.1021/acs.joc.7b00419

  日期：2017.5.5

  A straightforward strategy for the syntheses of curcumene and ar-himachalene is reported. Synthetic highlights include a catalytic and asymmetric vinylogous Mukaiyama reaction and a stereospecific hydrogenolysis of a tertiary benzylic center using Pd/C or Ni/Raney catalysts. Notably, using Ni/Raney, the stereoselectivity outcome (inversion vs retention) of the hydrogenolysis depends on the tertiary

  对于和姜黄的合成的直接战略AR-报道himachalene。合成的亮点包括使用Pd / C或Ni / Raney催化剂的催化和不对称乙烯基Mukaiyama反应和叔苄基中心的立体有择氢解。值得注意的是，使用Ni / Raney，氢解的立体选择性结果（转化相对于保留）取决于叔苄醇的取代。