methyl (-)-(5R,2E)-5-(tert-butyldimethylsilyloxy)hexenoate | 79414-02-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (-)-(5R,2E)-5-(tert-butyldimethylsilyloxy)hexenoate
• 英文别名: methyl (R,E)-5-(tert-butyldimethylsilyloxy)hex-2-enoate；methyl (2E,5R)-5-t-butyldimethylsiloxy-2-hexenoate；methyl (E,5R)-5-[tert-butyl(dimethyl)silyl]oxyhex-2-enoate
• CAS: 79414-02-1；121785-58-8；121785-61-3；133522-08-4；133522-10-8；133522-11-9；133522-09-5
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: JZACRADDHGBASF-RJCSOLBVSA-N

物化性质

• 沸点：
  282.4±23.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (-)-(5R,2E)-5-(tert-butyldimethylsilyloxy)hexenoate 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 以82%的产率得到ethyl (R,E)-5-(tert-butyldimethylsilyloxy)hex-2-enoate
  参考文献：
  名称：

  Synthesis of taurospongin A: a potent inhibitor of DNA polymerase and HIV reverse transcriptase, using π-allyltricarbonyliron lactone complexes

  摘要：

  已成功合成taurospongin A，关键步骤是使用一个π-烯丙基三羰基铁内酯复合物，以控制向该复合物侧链中的酮基单元高立体选择性的添加一个甲基。

  DOI：

  10.1039/b204994p
• 作为产物：
  描述：

  (R)-3-(tert-butyldimethylsilyloxy)-1-butanol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 methyl (-)-(5R,2E)-5-(tert-butyldimethylsilyloxy)hexenoate
  参考文献：
  名称：

  Synthesis of taurospongin A: a potent inhibitor of DNA polymerase and HIV reverse transcriptase, using π-allyltricarbonyliron lactone complexes

  摘要：

  已成功合成taurospongin A，关键步骤是使用一个π-烯丙基三羰基铁内酯复合物，以控制向该复合物侧链中的酮基单元高立体选择性的添加一个甲基。

  DOI：

  10.1039/b204994p

文献信息

• Synthesis of the Oviposition-Deterring Pheromone (ODP) inRhagoletis cerasi L. Preliminary communication
  作者：Beat Ernst、Beatrice Wagner

  DOI：10.1002/hlca.19890720122

  日期：1989.2.1

  For the assignment of the configuration at C(8) and C(15) of the natural oviposition-deterring pheromone 1 in Rhagoletis cerasi L., the four possible stereoisomers of 1 are synthesized. By condensing the C6 building blocks (5R)-4 and (5S)-4 with the boron enolates of the C10 building blocks (4S)-13 and (4R)-13, followed by decarboxylative dehydration, all stereoisomers of 16 are available (Scheme 5)

  为了赋予Rhogoletis cerasi L.中的天然产卵信息素1在C（8）和C（15）的构型，合成了四种可能的立体异构体1。通过将C 6结构单元（5 R）-4和（5 S）-4与C 10结构单元（4 S）-13和（4 R）-13的硼烯醇缩合，然后进行脱羧脱水，有16种立体异构体可供选择（方案5）。脱保护后，16的糖基化，随后形成牛磺酸酰胺，得到四个立体异构体（8 R，15 S）-1，（8 R，15 R）-1，（8 R，15 S）-1和（ 8 S，15 S）-1（方案6）。
• Total Synthesis of Grahamimycin A₁
  作者：Kazuo Ohta、Osamu Miyagawa、Hironori Tsutsui、Oyo Mitsunobu

  DOI：10.1246/bcsj.66.523

  日期：1993.2

  grahamimycin A1 (1). The O-7–C-14 fragment [(4S,5S,7R)- or (4R,5R,7R)-7-hydroxy-4,5-isopropylidenedioxyoctanoate] was synthesized from 4,6-dideoxy-α-D-xylo -hexopyranoside. Condensation of the both fragments, followed by deprotection at the terminal hydroxyl- and carboxyl-functions afforded the seco acids of the precursors of 1. While the reaction of the seco acids having 13S-configuration with diethyl azodicarboxylate

  (3R)- 和 (3S)-3-羟基丁酸酯分别转化为 (2E,5R)- 和 (2E,5S)-5-t-丁基二甲基甲硅烷氧基-2-己烯酸，对应于 O-1-C-6 Grahamimycin A1 (1) 的片段。O-7–C-14 片段 [(4S,5S,7R)- 或 (4R,5R,7R)-7-hydroxy-4,5-isopropylidenedioxyoctanoate] 由 4,6-dideoxy-α-D-合成木糖苷。两个片段的缩合，然后在末端羟基和羧基官能团上脱保护得到前体 1 的 seco 酸。 而具有 13S-构型的 seco 酸与偶氮二羧酸二乙酯和三苯基膦的反应在低浓度下提供相应的内酯产率，具有 13R-构型的癸二酸通过 Yamaguchi 程序的大环内酯化以 56% 的产率得到所需的内酯。
• Two Approaches to the Synthesis of the Macrodiolide Colletotriene
  作者：Dulce M. Muñoz、Stephen C. Passey、Thomas J. Simpson、Christine L. Willis、John B. Campbell、Richard Rosser

  DOI：10.1071/ch04038

  日期：——

  The first total syntheses of the 14-membered ring macrodilactone colletotriene are described. Starting from ethyl (R)-3-hydroxybutanoate, two synthetic strategies are compared which will enable the incorporation of deuterium at non-exchangeable sites for biosynthetic studies.

  本文介绍了 14 元环大内酯可乐三烯的首次全合成。以(R)-3-羟基丁酸乙酯为起点，比较了两种合成策略，这两种策略可以在非交换位点加入氘，用于生物合成研究。
• Stereoselective total synthesis of clonostachydiol
  作者：Udugu Ramulu、Dasari Ramesh、Singanaboina Rajaram、Sudina Purushotham Reddy、Kunuru Venkatesham、Yenamandra Venkateswarlu

  DOI：10.1016/j.tetasy.2012.01.014

  日期：2012.1

  A simple and efficient stereoselective synthesis of clonostachydiol was achieved using ethyl (R)-3-hydroxybutanoate 5 and methyl (R)-2-hydroxypropanoate 12 as readily available starting materials. The key steps involved in the synthesis were MacMillan alpha-hydroxylation, Horner-Wadsworth-Emmons (HWE) olefination, a Grignard reaction, and Hoveyda-Grubbs IInd generation catalyzed ring closing metathesis (RCM). (C) 2012 Elsevier Ltd. All rights reserved.
• Formal total synthesis of grahamimycin A1
  作者：Kazuo Ohta、Oyo Mitsunobu

  DOI：10.1016/s0040-4039(00)79484-6

  日期：1991.1

  (S)-t-Butyldimethylsiloxy-2-hexenoic acid and its (R)-isomer were prepared from (S)- and (R)-3-hydroxybutanoic acid esters, respectively. Condensation of the both isomers with 2-(ptoluenesulfonyl)ethyl (4S,5S,7R)-7-hydroxy-4,5-dimethylmethylenedioxyoctanoate, synthesized from methyl 4,6-dideoxy -alpha-D-xylo-hexopyranoside, gave the corresponding esters which were converted into precursors of seco acids of grahamimycin A1 with S or R configuration at the C-6 position (grahamimycin A1 numbering). The (6S)- and (6R)-isomers were respectively subjected to macrolactonization by the use of diethyl azodicarboxylate-triphenylphosphine system or Yamaguchi procedure to afford 11, 12-dihydroxy-grahamimycin A1 whose oxidation to grahamimycin A1 has already been reported.