(E)-(2S)-5-tert-butyldimethylsilyloxy-1,2-isopropylidene-3,5-hexadiene | 183795-48-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-(2S)-5-tert-butyldimethylsilyloxy-1,2-isopropylidene-3,5-hexadiene
• 英文别名: tert-butyl-[(3E)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]buta-1,3-dien-2-yl]oxy-dimethylsilane
• CAS: 183795-48-4
• 化学式: C₁₅H₂₈O₃Si
• 分子量: 284.471
• InChiKey: MPSYGHIYCSILJC-LXKVQUBZSA-N

物化性质

• 沸点：
  312.6±27.0 °C(predicted)
• 密度：
  0.955±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-(2S)-5-tert-butyldimethylsilyloxy-1,2-isopropylidene-3,5-hexadiene 在 三氟化硼乙醚 、 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.5h， 生成 6-((4R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-((E)-propenyl)tetrahydropyran-4-one
  参考文献：
  名称：

  Highly Substituted Tetrahydropyrones from Hetero-Diels−Alder Reactions of 2-Alkenals with Stereochemical Induction from Chiral Dienes

  摘要：

  A new method for the stereoselective synthesis of libraries of 2,3,5-trisubstituted tetrahydro-gamma-pyrones and the corresponding tetrahydropyran-4-ols is reported. Dienes with a chiral moiety at position 5 were synthesized starting from (triphenylphosphoranylidene)acetone. In hetero-Diels-Alder (HDA) reactions, especially with alpha,beta-unsaturated aldehydes, they induce diastereomeric ratios from 4:1 to 14:1. Through selective epimerization and reduction, further building blocks are available. These constitute ideal starting points for their use in the total synthesis of complex polyketide macrocycles, especially with the vinyl group available for metathetic coupling.

  DOI：

  10.1021/jo0488311
• 作为产物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 三乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 3.25h， 生成 (E)-(2S)-5-tert-butyldimethylsilyloxy-1,2-isopropylidene-3,5-hexadiene
  参考文献：
  名称：

  通过由（Salen）Co（II）催化剂和手性二烯引导的高度双立体选择性杂Diels-Alder反应正式合成3-Deoxy-D-manno-2-Octulosonic acid（KDO）。

  摘要：

  本文基于（Salen）Co催化的富电子二烯与乙醛酸乙酯之间的高度双立体选择性杂Diels-Alder反应，提出了3-脱氧-D-甘露糖-2-辛磺酸的正式全合成（II）络合物，是Diels-Alder反应的新催化剂。面部特定的硼氢化随后进行氧化处理会导致二醇系统在C-4和C-5处具有羟基的透-透水合安排。将C-5羟基的构型转化为12，然后缩酮形成，得到所需的目标二异亚丙基-2-脱氧-KDO甲基酯（18），可以根据文献方法将其转化为KDO。

  DOI：

  10.1021/jo971186w

文献信息

• Formal Synthesis of 3-Deoxy-<scp>d</scp>-manno-2-Octulosonic Acid (KDO) via a Highly Double-Stereoselective Hetero Diels−Alder Reaction Directed by a (Salen)Co^II Catalyst and Chiral Diene
  作者：Yun-Jin Hu、Xiao-Dong Huang、Zhu-Jun Yao、Yu-Lin Wu

  DOI：10.1021/jo971186w

  日期：1998.4.1

  This paper presents a formal total synthesis of 3-deoxy-D-manno-2-octulosonic acid (KDO) based on a highly double-stereoselective hetero Diels-Alder reaction between an electron-rich diene and ethyl glyoxylate catalyzed by (Salen)Co(II) complex, a new catalyst for Diels-Alder reactions. A facial specific hydroboration followed by oxidative workup leads to a diol system with the trans-diequatorial arrangement

  本文基于（Salen）Co催化的富电子二烯与乙醛酸乙酯之间的高度双立体选择性杂Diels-Alder反应，提出了3-脱氧-D-甘露糖-2-辛磺酸的正式全合成（II）络合物，是Diels-Alder反应的新催化剂。面部特定的硼氢化随后进行氧化处理会导致二醇系统在C-4和C-5处具有羟基的透-透水合安排。将C-5羟基的构型转化为12，然后缩酮形成，得到所需的目标二异亚丙基-2-脱氧-KDO甲基酯（18），可以根据文献方法将其转化为KDO。
• Chiral dienes from enantiomerically pure enones. Highly stereoselective intramolecular Diels–Alder reaction involving ethenesulfonates
  作者：Guido Galley、Michael Pätzel

  DOI：10.1039/p19960002297

  日期：——

  Chiral dienes 2, easily prepared from alpha,beta-unsaturated gamma-alkoxy ketones, are subjected to inter- and intramolecular Diels-Alder reactions, Intermolecular cycloadditions of dienes 2 with 4-phenyl-1,2,4-triazole-3,5(2H)-dione 3 are found to be diastereoselective, Thermal or high pressure-induced intramolecular cycloadditions of trienes 8, featuring a sulfonate moiety connecting a diene and a dienophile, are found to proceed with high diastereoselectivity to give sultones 11 and 12. An interesting domino process is observed when enone 5 is reacted with sodium hydride. In this reaction sequence, the decahydropyrano [2,3,4-de]chromene derivative 15 was formed, NMR spectroscopic studies allowed the assignments of the configurations of the bi- and tri-cyclic products.
• Highly Substituted Tetrahydropyrones from Hetero-Diels−Alder Reactions of 2-Alkenals with Stereochemical Induction from Chiral Dienes
  作者：Eelco Ruijter、Heike Schültingkemper、Ludger A. Wessjohann

  DOI：10.1021/jo0488311

  日期：2005.4.1

  A new method for the stereoselective synthesis of libraries of 2,3,5-trisubstituted tetrahydro-gamma-pyrones and the corresponding tetrahydropyran-4-ols is reported. Dienes with a chiral moiety at position 5 were synthesized starting from (triphenylphosphoranylidene)acetone. In hetero-Diels-Alder (HDA) reactions, especially with alpha,beta-unsaturated aldehydes, they induce diastereomeric ratios from 4:1 to 14:1. Through selective epimerization and reduction, further building blocks are available. These constitute ideal starting points for their use in the total synthesis of complex polyketide macrocycles, especially with the vinyl group available for metathetic coupling.