1-(trimethylsilyloxy)-1,3-pentadiene | 72237-32-2

• 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-(trimethylsilyloxy)-1,3-pentadiene
• 英文别名: Trimethyl(penta-1,3-dienoxy)silane
• CAS: 72237-32-2
• 化学式: C₈H₁₆OSi
• 分子量: 156.3
• InChiKey: DGKGZUGARUIJKA-UHFFFAOYSA-N

物化性质

• 沸点：
  160.0±8.0 °C(Predicted)
• 密度：
  0.822±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.93
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(三甲基硅氧基)丙烯 、 1-(trimethylsilyloxy)-1,3-pentadiene 在 ammonium cerium(IV) nitrate 、 calcium carbonate 作用下， 以 乙腈 为溶剂， 以47%的产率得到(E)-4-Methyl-6-oxo-hept-2-enal
  参考文献：
  名称：

  硝酸铈铵中的γ选择性促进了甲硅烷基二烯醇醚向甲硅烷基烯醇醚的氧化加成

  摘要：

  三甲基甲硅烷基二烯醇醚很容易被硝酸铈铵氧化，生成α-羰基烯丙基自由基，该自由基能够以很高的γ区域选择性加成烯醇式碳-碳双键，从而可用于合成6-氧代-α， β-不饱和羰基化合物。

  DOI：

  10.1016/s0040-4039(00)61663-5
• 作为产物：
  描述：

  三甲基氯硅烷 、 戊-3-烯醛 在 三乙胺 、 zinc(II) chloride 作用下， 反应 24.0h， 以40%的产率得到1-(trimethylsilyloxy)-1,3-pentadiene
  参考文献：
  名称：

  Makin, S. M.; Kruglikova, R. I.; Popova, T. P., Journal of Organic Chemistry USSR (English Translation), 1982, p. 1001 - 1003

  摘要：

  DOI：

文献信息

• Reactions of Trimethylsilyl Dienol Ethers with Palladium(II) Salts:  Formation of Formyl-Substituted η³-Allylpalladium Complexes and 4-Acyloxy-2-Alkenals
  作者：Björn C. Söderberg、Angela K. Berry、Paula C. Jones

  DOI：10.1021/om971048x

  日期：1998.3.1

  to excellent yield. In contrast, using palladium diacetate as the palladium(II) source produces 4-acetyloxy-substituted 2-alkenals. Excellent stereoselection in favor of the E-alkenal is usually observed. The corresponding benzoic acid esters can be prepared, with similar stereoselection, using 1-(trimethylsilyloxy)-1,3-dienes and palladium diacetate in the presence of an excess sodium benzoate.

  的反应的无环的1-（三甲基甲硅烷）-1,3-二烯与二氯化双（乙腈）钯，在苯，得到甲酰基取代的η 3种以良好至优异的产量π-烯丙基配合物。相反，使用二乙酸钯作为钯（II）源会生成4-乙酰氧基取代的2-烯醛。通常观察到有利于E-链烯醛的优异的立体选择。可以在存在过量苯甲酸钠的情况下，使用1-（三甲基甲硅烷氧基）-1，3-二烯和二乙酸钯，以相似的立体选择制备相应的苯甲酸酯。
• Iqbal, Javed; Khan, M. Amin, Synthetic Communications, 1989, vol. 19, # 3and4, p. 515 - 522
  作者：Iqbal, Javed、Khan, M. Amin

  DOI：——

  日期：——
• Primke, Hartmut; Sarin, Gurdeep S.; Kohlstruk, Stephan, Chemische Berichte, 1994, vol. 127, # 6, p. 1051 - 1064
  作者：Primke, Hartmut、Sarin, Gurdeep S.、Kohlstruk, Stephan、Adiwidjaja, Gunadi、Meijere, Armin de

  DOI：——

  日期：——
• Reactions of co-ordinated ligands. Part 50. The synthesis of functionalised η³-allyl complexes of molybdenum and their conversion into η⁴-s-trans-1,3-dienes
  作者：Stephen A. Benyunes、Alessandra Binelli、Michael Green、Michael J. Grimshire

  DOI：10.1039/dt9910000895

  日期：——

  Reaction of the labile bis(acetonitrile) complexes [Mo(NCMe)2(CO)2(eta-5-L)][BF4] (L = C9H7 1 or C5Me5 2) with the 1-trimethylsilyloxybuta-1,3-dienes Me3SiOCH = CR1CH = CHR2 (R1 = R2 = H; R1 = Me, R2 = H; R1 = H, R2 = Me) results in initial co-ordination of the diene followed by a rapid desilylation affording the 4-oxo-functionalised allyls [Mo(eta-3-CR2R3CHCR1CHO)(CO)2(eta-5-L)] 4 and 6-9. Complexes 4 and 6-9 are generated in the form of isomeric mixtures, arising through syn-anti isomerism at C2 of the allyl ligand together with the presence of non-interconvertible exo and endo orientations for the latter with respect to the metal fragment. Addition of Ph3P = CH2 to 6 (R1 = R2 = R3 = H) and 7 (R1 = Me, R2 = R3 = H) effects smooth conversion into the eta-3-pentadienyl complexes [Mo(eta-3-CR2R3CHCR1CHCH2)(CO)2(eta-5-C5Me5)] 11 (R1 = R2 = R3 = H) and 12 (R1 = Me, R2 = R3 = H). The low-temperature (-78-degrees-C) protonation of compounds syn-6-8 using CF3SO3H results in a quantitative transformation into the s-trans-diene cations [Mo(eta-4-s-trans-trans-HOCHCR1CHCR2R3)-(CO)2(eta-5-C5Me5)][CF3SO3] 13 (R1 = R2 = R3 = H), 14 (R1 = Me, R2 = R3 H) and 15 (R1 = R3 = H, R2 = Me), characterised in situ by H-1 NMR spectroscopy. Above -30-degrees-C, 13-15 undergo an irreversible rearrangement in solution to the corresponding s-cis diene cations. Deprotonation of 13-15 by treatment with NEt3 regenerates the syn isomers of 6-8, whilst the s-cis diene cations produce only the anti species under the same conditions. These results are interpreted in terms of an overall retention of stereochemistry of the C4 ligand throughout these manipulations. The eta-3-pentadienyl complexes 11 and 12 undergo analogous transformations upon addition of CF3SO3H producing the thermally unstable s-trans-diene cations [Mo(eta-4-s-trans-trans-MeCHCRCHCH2)(CO)2(eta-5-C5Me5)][CF3SO3] 16 (R = H) and 17 (R = Me), which are likewise converted into their s-cis isomers at temperatures in excess of -20-degrees-C.
• γ-selectivity in the ceric ammonium nitrate promoted oxidative addition of silyl dienol ethers to silyl enol ethers
  作者：Anna Belli Paolobelli、David Latini、Renzo Ruzziconi

  DOI：10.1016/s0040-4039(00)61663-5

  日期：1993.1

  Trimethylsilyl dienol ethers are easily oxidized by ceric ammonium nitrate to give α-carbonylallyl radicals which are able to add to enolic carbon-carbon double bonds with very high γ regioselectivity, allowing the method to be applied to the synthesis of 6-oxo-α,β-unsaturated carbonyl compounds.

  三甲基甲硅烷基二烯醇醚很容易被硝酸铈铵氧化，生成α-羰基烯丙基自由基，该自由基能够以很高的γ区域选择性加成烯醇式碳-碳双键，从而可用于合成6-氧代-α， β-不饱和羰基化合物。