2-[(1S,2R,5R)-2-ethenyl-5-triethylsilyloxycyclopentyl]acetaldehyde | 932391-37-2

• 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: 2-[(1S,2R,5R)-2-ethenyl-5-triethylsilyloxycyclopentyl]acetaldehyde
• CAS: 932391-37-2
• 化学式: C₁₅H₂₈O₂Si
• 分子量: 268.472
• InChiKey: BJASVWDXONOYIQ-SOUVJXGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(1S,2R,5R)-2-ethenyl-5-triethylsilyloxycyclopentyl]acetaldehyde 在 chromium(VI) oxide 、 盐酸 、 sodium chlorite 、 2-甲基-2-丁烯 、 pyridine-SO3 complex 、 bis(cyclohexanyl)borane 、 sodium hexamethyldisilazane 、 4-甲基苯磺酸吡啶 、 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 phosphate buffer 、 乙醇 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 12-羟基茉莉酸
  参考文献：
  名称：

  First total synthesis of tuberonic acid

  摘要：

  A vinyl group as an acetic acid side chain was attached to the optically active monoacetate of 4-cyclopentene-1,3-diol with CH2=CHMgBr, LiCl and a CuCN catalyst to produce the S(N)2-type product, from which the full carbon skeleton of tuberonic acid was constructed through Mitsunobu inversion, Claisen rearrangement, and Wittig reaction. At the last stage, the THP protective group was removed with MgBr2 in Et2O. The diastereomeric ratio of tuberonic acid and the trans isomer was 92:8 by H-1 NMR spectroscopy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.01.035
• 作为产物：
  描述：

  (3aS,4R,6aR)-4-ethenyl-3,3a,4,5,6,6a-hexahydrocyclopenta[b]furan-2-one 在 lithium aluminium tetrahydride 、 草酰氯 、 米帕明 、 二甲基亚砜 、 三乙胺 作用下， 生成 2-[(1S,2R,5R)-2-ethenyl-5-triethylsilyloxycyclopentyl]acetaldehyde
  参考文献：
  名称：

  First total synthesis of tuberonic acid

  摘要：

  A vinyl group as an acetic acid side chain was attached to the optically active monoacetate of 4-cyclopentene-1,3-diol with CH2=CHMgBr, LiCl and a CuCN catalyst to produce the S(N)2-type product, from which the full carbon skeleton of tuberonic acid was constructed through Mitsunobu inversion, Claisen rearrangement, and Wittig reaction. At the last stage, the THP protective group was removed with MgBr2 in Et2O. The diastereomeric ratio of tuberonic acid and the trans isomer was 92:8 by H-1 NMR spectroscopy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.01.035

文献信息

• Synthesis of the amino acid conjugates of epi-jasmonic acid
  作者：N. Ogawa、Y. Kobayashi

  DOI：10.1007/s00726-011-0925-z

  日期：2012.5

  The TES ether of the C6-hydroxy derivative of naturally occurring epi-jasmonic acid (epi-JA) was designed as epimerization-free equivalent of epi-JA. The TES ether was synthesized from (1R,4S)-4-hydroxycyclopent-2-enyl acetate in 13 steps. The acid part of the ether was activated with ClCO2Bui and subjected to condensation with l-amino acid at room temperature for 48 h. The TES group in the condensation

  的TES醚的天然存在的C6羟基衍生物的外延-jasmonic酸（EPI -ja）被设计为自由差向异构当量的外延-ja。由（1 R，4 S）-4-羟基环戊-2-烯基乙酸酯经13个步骤合成TES醚。醚的酸部分用ClCO激活2卜我并进行缩合升-氨基在室温下酸48小时。在HCO 2 H中（0°C，30分钟）除去缩合产物中的TES基团，然后用Jones试剂（丙酮，0°C，30分钟）氧化所得的羟基，以提供Epi的氨基酸缀合物。-JA 所检查的氨基酸为1-异亮氨酸，1-亮氨酸，1-丙氨酸，1-缬氨酸和d -allo-异亮氨酸，与反式异构体相比，其缀合物的收率为48-68％，非对映异构体纯度为89-96％。类似地，将epi -JA的可能的三种立体异构体与1-异亮氨酸成功缩合，以高收率产生相应的立体异构体。
• Stereoselective synthesis of epi-jasmonic acid, tuberonic acid, and 12-oxo-PDA
  作者：Hisato Nonaka、Narihito Ogawa、Noriaki Maeda、Yong-Gang Wang、Yuichi Kobayashi

  DOI：10.1039/c0ob00218f

  日期：——

  epi-Jasmonic acid (epi-JA) and tuberonic acid (TA) were synthesized from the key aldehyde, all cis-2-(2-hydroxy-5-vinylcyclopentyl)acetaldehyde (14), which was in turn prepared stereoselectively from the (1R)-acetate of 4-cyclopentene-1,3-diol (10) through SN2-type allylic substitution with CH2CHMgBr followed by Mitsunobu inversion, Eschenmoser–Claisen rearrangement, and regioselective Swern oxidation

  表-茉莉酸 （Epi -JA） 和 胡椒酸 （TA）是由关键醛合成的，所有 顺-2-（2-羟基-5-乙烯基环戊基）乙醛（14），其又由（1R）-乙酸的乙酸酯立体选择性地制备。4-环戊烯-1,3-二醇（10）通过用CH 2 CHMgBr进行S N 2型烯丙基取代，然后进行Mitsunobu转化，埃申摩瑟–相应的bis-TES醚（13）的克莱森重排和区域选择性Swern氧化。醛14与[Ph 3 P（CH 2）Me] +的维蒂希反应溴−随后进行氧化Epi -JA（3）对反式异构体的立体选择性。相似地，TA（5）被合成。此外，上述发现已成功地用于提高以前合成的12-氧代PDA（1）。
• Strategy for synthesis of the isoleucine conjugate of epi-jasmonic acid
  作者：Narihito Ogawa、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2008.09.144

  日期：2008.12

  The TES ether of 2-((1R,2S,3R)-3-hydroxy-2-((Z)-pent-2-enyl)cyclopentyl)acetic acid (5, equal to the reduction product of epi-jasmonic acid) derived from (1R,4S)-4-hydroxycyclopent-2-enyl acetate (19) in 13 steps was activated by using isobutyl chloroformate and was subjected to condensation with isoleucine at room temperature for 48 h. The product was desilylated and oxidized to the isoleucine conjugate of epi-jasmonic acid in 68% yield over three steps. Similarly, allo-isoleucine conjugate of epi-jasmonic acid and three isoleucine conjugates of ent-epi-jasmonic acid, jasmonic acid, and ent-jasmonic acid were synthesized. (C) 2008 Elsevier Ltd. All rights reserved.
• First total synthesis of tuberonic acid
  作者：Hisato Nonaka、Yong-Gang Wang、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2007.01.035

  日期：2007.3

  A vinyl group as an acetic acid side chain was attached to the optically active monoacetate of 4-cyclopentene-1,3-diol with CH2=CHMgBr, LiCl and a CuCN catalyst to produce the S(N)2-type product, from which the full carbon skeleton of tuberonic acid was constructed through Mitsunobu inversion, Claisen rearrangement, and Wittig reaction. At the last stage, the THP protective group was removed with MgBr2 in Et2O. The diastereomeric ratio of tuberonic acid and the trans isomer was 92:8 by H-1 NMR spectroscopy. (c) 2007 Elsevier Ltd. All rights reserved.