methyl (1S,4R)-4-acetoxy-2-cyclopentenylcarbonate | 138318-67-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: methyl (1S,4R)-4-acetoxy-2-cyclopentenylcarbonate
• 英文别名: (1S-cis)-2-Cyclopenten-1,4-diol 1-(Methylcarbonate) 4-Acetate；(1S-cis)-2-Cyclopentene-1,4-diol 1-(Methylcarbonate) 4-Acetate；[(1R,4S)-4-methoxycarbonyloxycyclopent-2-en-1-yl] acetate
• CAS: 138318-67-9
• 化学式: C₉H₁₂O₅
• 分子量: 200.191
• InChiKey: CKBUYKSGKFNNEE-JGVFFNPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (1S,4R)-4-acetoxy-2-cyclopentenylcarbonate 在 四氧化锇 、 sodium hydride 、 对甲苯磺酸 、 N-甲基吗啉氧化物 、 potassium iodide 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 19.5h， 生成 methyl 1-O-acetyl-5-deoxy-2,3-O-isopropylidene-β-DL-ribo-carbahexofuranuronate
  参考文献：
  名称：

  碳环正弦菌素及其C-5差向异构体的聚合合成

  摘要：

  描述了碳环正弦菌素 2 及其 C5 差向异构体 3 的聚合合成。我们合成的主要特点包括使用市售的 L-甲硫氨酸和现成的 (1R, 4S)-4-羟基-2-环戊烯基乙酸酯作为起始材料、交叉复分解偶联、酶动力学拆分和施陶丁格还原。目前的合成是灵活的，因此可以方便地合成各种用于生物学评价的碳环 SIN 类似物。

  DOI：

  10.1002/ejoc.201402812
• 作为产物：
  描述：

  (1S,4R)-顺式-4-乙酰氧基-2-环戊烯-1-醇 、 氯甲酸甲酯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 methyl (1S,4R)-4-acetoxy-2-cyclopentenylcarbonate
  参考文献：
  名称：

  碳环正弦菌素及其C-5差向异构体的聚合合成

  摘要：

  描述了碳环正弦菌素 2 及其 C5 差向异构体 3 的聚合合成。我们合成的主要特点包括使用市售的 L-甲硫氨酸和现成的 (1R, 4S)-4-羟基-2-环戊烯基乙酸酯作为起始材料、交叉复分解偶联、酶动力学拆分和施陶丁格还原。目前的合成是灵活的，因此可以方便地合成各种用于生物学评价的碳环 SIN 类似物。

  DOI：

  10.1002/ejoc.201402812

文献信息

• Nickel/Zinc Chloride-Promoted Domino Reaction of Enynes and Enones Including Unstrained CC Bond Cleavage
  作者：Kaori Ambe-Suzuki、Yukari Ohyama、Naohiro Shirai、Shin-ichi Ikeda

  DOI：10.1002/adsc.201100770

  日期：2012.3.16

  Unstrained CC bond cleavage proceeds during the domino reaction of enynes and enones that includes successive CC bond formation under the nickel/zinc/zinc chloride system. The cleavage occurs through β‐syn‐elimination of the 1,3‐dicarbonyl part. In addition, β‐carbon elimination is selective, unlike the β‐hydrogen elimination in the presence of excess zinc chloride.

  非应变Ç 烯炔和烯酮的多米诺反应，其包括连续℃持续C键的裂解前进镍/锌/氯化锌系统下C键的形成。裂解是通过1，3-二羰基部分的β同步消除而发生的。另外，β-碳的消除是选择性的，这与在过量氯化锌存在下的β-氢的消除不同。
• Synthesis of purine substituted cyclopentene derivatives
  申请人：Glaxo Inc.

  公开号：US05126452A1

  公开（公告）日：1992-06-30

  This invention relates to new process for preparing certain optically active purine substituted cyclopentene derivatives and novel intermediates used in this process. In particular, the invention concerns the synthesis of the 1R-cis isomer of carbovir, (1R-cis)-amino-1,9-dihydro-9-[4-(hydroxymethyl)-2-cyclopenten-1-yl]-6H-pur in-6-one, an antiviral agent, and certain intermediates.

  本发明涉及一种制备特定光学活性嘌呤取代环戊烯衍生物和用于该过程的新型中间体的新工艺。具体地，本发明涉及合成卡波韦尔的1R-cis异构体，即(1R-cis)-氨基-1,9-二氢-9-[4-(羟甲基)-2-环戊烯-1-基]-6H-嘌呤-6-酮，一种抗病毒药物，以及某些中间体。
• Asymmetric Total Syntheses of (-)- and (+)-Strychnine and the Wieland-Gumlich Aldehyde
  作者：Steven D. Knight、Larry E. Overman、Garry Pairaudeau

  DOI：10.1021/ja00126a017

  日期：1995.5

  The first asymmetric total syntheses of (-)-strychnine, ent-strychnine, and the Wieland-Gumlich aldehyde are described with full experimental details. The total synthesis of (-)-strychnine was realized in 24 steps and 3% overall yield from (1R,4S)-(+)-4-hydroxy-2-cyclopentenyl acetate (28). This synthesis fully controls the six stereogenic centers and forms the C(20) double bond of (-)-strychnine with high diastereoselection (>20:1). In the first stage of the synthesis, the (R)-cyclopentenylstannane 8 is prepared in nine steps and 30% overall yield (40% with one recycle of 38) as summarized in Scheme 4. Palladium-catalyzed carbonylative coupling of 8 with the 2-iodoaniline derivative 7 provides enone 6, which is converted to the 2-azabicyclo[3.2.1]octane 5 in seven additional steps. This latter sequence proceeds in 36% overall yield (Scheme 6). The central step of the total synthesis is aza-Cope-Mannich rearrangement of 5 which proceeds in 98% yield to form the pentacyclic intermediate 4 (Scheme 7). In five additional steps 4 is converted to the Wieland-Gumlich aldehyde 2, which is the ultimate precursor of (-)strychnine. A slight modification of this synthesis strategy allowed ent-strychnine to be prepared and provided the first samples of this unnatural enantiomer for pharmacological studies (Scheme 8). The efficiency and conciseness of this synthesis provide an important benchmark of the power of the aza-Cope rearrangement-Mannich reaction to solve formidable problems in alkaloid construction.
• Synthesis applications of cationic aza-Cope rearrangements. 26. Enantioselective total synthesis of (-)-strychnine
  作者：Steven D. Knight、Larry E. Overman、Garry Pairaudeau

  DOI：10.1021/ja00073a057

  日期：1993.10
• Ni-Catalyzed, ZnCl₂-Assisted Domino Coupling of Enones, Alkynes, and Alkenes
  作者：Shin-ichi Ikeda、Reiko Sanuki、Hiroko Miyachi、Hitoshi Miyashita、Masami Taniguchi、Kazunori Odashima

  DOI：10.1021/ja047580a

  日期：2004.8.1

  A Ni(O)/ZnCl2 system effectively promotes the coupling of enones and alkene-tethered alkynes. In the reaction with 1,6-enynes, the oxidative cyclization of Ni(O) species on enones across the alkyne part followed by ZnCl2-promoted cleavage generates alkenylnickel intermediates. Subsequent migratory insertion of the tethered alkene occurs with 5-exo-cyclization. When the resulting sigma-alkylnickel intermediates have beta-hydrogen atoms, the reaction terminates by beta-hydrogen elimination to provide cyclopentane derivatives. On the other hand, a sigma-alkylnickel intermediate that does not have beta-hydrogen atoms undergoes the insertion of a second alkene unit to cause a domino effect via a three-fold C-C bond formation process with and without the cleavage of one C-C bond.