((E)-3-(methoxymethylene)pent-1-en-2-yloxy)trimethylsilane | 177217-41-3

• 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: ((E)-3-(methoxymethylene)pent-1-en-2-yloxy)trimethylsilane
• 英文别名: [(3E)-3-(methoxymethylidene)pent-1-en-2-yl]oxy-trimethylsilane
• CAS: 177217-41-3
• 化学式: C₁₀H₂₀O₂Si
• 分子量: 200.353
• InChiKey: JWOIUILYKFXBHK-CSKARUKUSA-N

物化性质

• 沸点：
  79-84 °C(Press: 14 Torr)
• 密度：
  0.869±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  ((E)-3-(methoxymethylene)pent-1-en-2-yloxy)trimethylsilane 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 四乙基氯化铵 、 potassium carbonate 、 三苯基膦 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  Construction of the tricyclic benzoquinolizine ring system by combination of a tandem Mannich-Michael reaction with a Heck reaction

  摘要：

  Tetrahydro- and hexahydrobenzo[a]quinolizinones can be built up efficiently by means of a two step reaction sequence consisting of a tandem Mannich-Michael reaction and a Heck reaction. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00494-2
• 作为产物：
  描述：

  2-ethyl-3-oxobutanal sodium salt 在 乙酰氯 作用下， 以 乙醚 、 环己烷 为溶剂， 反应 1.25h， 生成 ((E)-3-(methoxymethylene)pent-1-en-2-yloxy)trimethylsilane
  参考文献：
  名称：

  通过一个普通的中间体进行品尼明和抗毒素-α的全合成。关于Anatoxin-a残局的警告

  摘要：

  本文描述了天然存在的生物碱pinnamine（的全合成1）和类毒素-A（2从公共对映体纯中间体（）7容易从焦谷氨酸）。对映体纯品己胺的合成分10步进行，总收率为4.8％，而且路线灵活，足以立体控制进入天然产物的非天然同类物（5-表位-哌啶胺）。N-酰基亚胺离子的分子内反应是品尼明和抗毒素-α合成的关键步骤。然而，与文献先例形成鲜明对比的是，在氮的反应过程中观察到完全消旋-酰基亚胺离子导致后者的生物碱。

  DOI：

  10.1021/jo0506682

文献信息

• Asymmetric synthesis of highly functionalized tetracyclic indole bases embodying the basic skeleton of yohimbine- and reserpine type alkaloids
  作者：Ralf Lock、Herbert Waldmann

  DOI：10.1016/0040-4039(96)00388-7

  日期：1996.4

  Schiff bases derived from tryptophan methyl ester react with differently substituted electron-rich siloxy dienes in the presence of achiral or chiral boric acid esters to give enaminones 5 and 6 with high diastereomer ratios (up to >98:2). These intermediates are converted into highly functionalized indoloquinolizines 14 and 15 by means of a new method which employs the transformation of vinylogous

  衍生自色氨酸甲酯的席夫碱在非手性或手性硼酸酯的存在下与不同取代的富电子的甲硅烷氧基二烯反应，得到具有高非对映异构体比率（最高> 98：2）的烯胺酮5和6。通过一种新方法将这些中间体转化为高度官能化的吲哚并喹唑酮14和15，该方法采用乙烯基酰胺转化为乙烯基氯甲基胺并将其随后转化为乙烯基亚氨基酰氯作为关键步骤。
• Blaeser, Edwin; Kolar, Patrik; Fenske, Dieter, European Journal of Organic Chemistry, 1999, # 1, p. 329 - 334
  作者：Blaeser, Edwin、Kolar, Patrik、Fenske, Dieter、Goesmann, Hellmut、Waldmann, Herbert

  DOI：——

  日期：——
• Three-Step Access to the Tricyclic Benzo[<i>a</i>]quinolizine Ring System
  作者：Stephan Kirschbaum、Herbert Waldmann

  DOI：10.1021/jo972035w

  日期：1998.7.1

  Access to the tricyclic benzo[a]quinolizine ring system, which forms the characteristic framework of alkaloids of the berberine and emetine type, is readily obtained by a three-step reaction sequence. This sequence includes the formation of a Schiff base, derived from a 2-bromo-substituted phenylethylamine, and its tandem Mannich/conjugate addition reaction with an electron-rich silyloxy diene forming an intermediate enaminone, which subsequently undergoes a Heck-type cyclization. Highest yields of the tandem Mannich/conjugate addition for aromatic Schiff bases and formaldehyde imines are observed in the presence of ZnCl2 in THF, whereas aromatic imines give the best results in the presence of EtAlCl2 in CH2Cl2. The best results for the Heck-type cyclizations are obtained either under heterogeneous conditions in the presence of K2CO3/NEt4Cl at 120 degrees C in DMF or in refluxing toluene or under homogeneous conditions at 100 degrees C in DMF in the presence of NEt-(i-Pr)(2). Depending on the substitution pattern of the diene and the steric demand of the base employed in the Heck cyclization, benzo[a]quinolizines carrying a double bond in the 11b,1- or 3,4-position or in an exocyclic position are obtained with fair to good results. A mechanistic rationale for this behavior is proposed. If chiral amines, e.g., derived from an amino acid ester, are employed in the three-step reaction sequence, chiral tricyclic benzo[a]quinolizines become accessible in a straightforward manner.
• Enantioselective Construction of Highly Functionalized Indoloquinolizines—congeners to Polycyclic Indole Alkaloids
  作者：Ralf Lock、Herbert Waldmann

  DOI：10.1002/chem.19970030122

  日期：1997.1

  AbstractIndolo[2,3‐a]quinolizines have been prepared in enantiomerically pure form by a very short and efficient synthetic sequence consisting of a) formation of imines of tryptophan esters, b) their enantioselective reaction with substituted silyloxydienes mediated by a chiral or an achiral boron Lewis acid, and c) subsequent ring closure initiated by conversion of the generated vinylogous amides into vinylogous imidoyl chlorides. With this strategy various substituents can be incorporated directly into the 1‐position of the heterocyclic framework of complex indole alkaloids by the choice of an appropriate silyloxydiene, so that subsequent derivatization of the alkaloid precursor at this position is rendered unnecessary.