[2S]-1-benzyloxy-2-methyl-3-[(trimethylsilyl)methyl]-but-3-ene | 203454-47-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [2S]-1-benzyloxy-2-methyl-3-[(trimethylsilyl)methyl]-but-3-ene
• 英文别名: (R)-(4-(benzyloxy)-3-methyl-2-methylenebutyl)trimethylsilane；trimethyl-[(3R)-3-methyl-2-methylidene-4-phenylmethoxybutyl]silane
• CAS: 203454-47-1
• 化学式: C₁₆H₂₆OSi
• 分子量: 262.467
• InChiKey: BIJXLWFSMYPESD-AWEZNQCLSA-N

物化性质

• 沸点：
  305.9±30.0 °C(Predicted)
• 密度：
  0.899±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• 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：

  [2S]-1-benzyloxy-2-methyl-3-[(trimethylsilyl)methyl]-but-3-ene 在 氨 、 calcium 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到(2R)-2-methyl-3-(trimethylsilylmethyl)but-3-en-1-ol
  参考文献：
  名称：

  Studies for the enantiocontrolled preparation of substituted tetrahydropyrans: applications for the synthesis of leucascandrolide A macrolactone

  摘要：

  Strategies for the stereocontrolled preparations of 2,6-cis- and 2,6-trans-substituted tetrahydropyrans have been devised. These studies have explored methodology for asymmetric induction in S-E' reactions using chiral 1,3,2-diazaborolidine controllers. Reactions with aldehydes at -78 degrees C yield nonracemic 1,5-diols for chemoselective internal backside displacements. This concept is developed as a flexible and reliable strategy in studies toward leucascandrolide A macrolactone 2 via the sequential applications of S-E' reactions leading to the C-1-C-9 aldehyde 14, and the bis-tetrahydropyran 59, respectively. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.020
• 作为产物：
  描述：

  (4R)-4-benzyl-3-[(2S)-2-methyl-3-phenylmethoxypropanoyl]-1,3-oxazolidin-2-one 在 magnesium 、 samarium(III) trifluoromethanesulfonate 作用下， 以 四氢呋喃 为溶剂， 反应 4.5h， 生成 [2S]-1-benzyloxy-2-methyl-3-[(trimethylsilyl)methyl]-but-3-ene
  参考文献：
  名称：

  对映体全合成altohyrtin C（海绵抑素2）

  摘要：

  描述了海绵吡喃大环内酯的首个全合成，altohyrtinC。聚合合成策略依赖于区域选择性大内酯化，两个主要合成片段的立体选择性Wittig偶联，复杂的抗羟醛反应以连接C 1 –C 15和C 16 –C 28螺酮基区域，以及端基砜磺酰化以进行连接C 29 –C 37和C 38 –C 43吡喃区。C 44 –C 51的合并在合成的最后阶段，侧链为在该药理学重要区域中构建变体建立了可行的途径。方法的发展途中对总合成包括1,5-反-选择性甲基酮醇醛缩合反应和非对映选择性方法的路易斯酸介导的β - Ç -glycosidation。合成的完成证实了altohyrtin系列中提出的立体化学分配，并确定了altohyrtin和海绵体抑素海洋大环内酯类的身份。

  DOI：

  10.1016/s0040-4020(99)00438-x

文献信息

• Elaboration of Sterically Hindered δ-Lactones through Ring-Closing Metathesis: Application to the Synthesis of the C1–C27 Fragment of Hemicalide
  作者：Camille Lecourt、Srikanth Boinapally、Sabrina Dhambri、Guillaume Boissonnat、Christophe Meyer、Janine Cossy、François Sautel、Georges Massiot、Janick Ardisson、Geoffroy Sorin、Marie-Isabelle Lannou

  DOI：10.1021/acs.joc.6b02208

  日期：2016.12.16

  The synthesis of the C1–C27 fragment of hemicalide, a marine metabolite displaying a unique potent antiproliferative activity, has been accomplished. The synthetic approach highlights a remarkably efficient ring-closing metathesis reaction catalyzed by Nolan ruthenium indenylidene complexes to elaborate the highly substituted δ-lactone framework.

  hemicalide的C1-C27片段（一种具有独特的有效抗增殖活性的海洋代谢物）的合成已完成。合成方法强调了由Nolan钌茚并亚烷基配合物催化的高效率的闭环复分解反应，以阐明高度取代的δ-内酯骨架。
• Enantioselective Synthesis of Altohyrtin C(Spongistatin 2): Synthesis of the AB- and CD-Spiroketal Subunits
  作者：David A. Evans、Paul J. Coleman、Luiz Carlos Dias

  DOI：10.1002/anie.199727381

  日期：1997.1.7
• Allyltrichlorostannane additions to chiral aldehydes
  作者：Luiz Carlos Dias、Débora Ribeiro dos Santos、Leonardo José Steil

  DOI：10.1016/s0040-4039(03)01713-1

  日期：2003.9

  Chiral and achiral allyltrichlorostannanes reacted with chiral beta-alkoxy and syn and anti alpha-methyl-beta-alkoxy aldehydes to give the corresponding homoallylic alcohols with moderate to high diastereoselectivities. (C) 2003 Elsevier Ltd. All rights reserved.
• Dias, Luiz C.; Meira, Paulo R. R., Synlett, 2000, # 1, p. 37 - 40
  作者：Dias, Luiz C.、Meira, Paulo R. R.

  DOI：——

  日期：——
• On 1,4-diastereoselectivity in the chiral allylsilane addition to chiral α-substituted aldehydes
  作者：Luiz C. Dias、Rosana Giacomini

  DOI：10.1016/s0040-4039(98)01066-1

  日期：1998.7

  Chiral allylsilane 2 reacted with chiral alpha-substituted aldehydes to afford the corresponding 1,4-syn-products with good diastereoselectivities. The best selectivities are observed when the reactions are carried out by transmetallation of allylsilane using Tin (IV) chloride in CH2Cl2, at -78 degrees C, before addition of the aldehydes. (C) 1998 Elsevier Science Ltd. All rights reserved.