(8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one | 1029316-89-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one
• 英文别名: (R)-8-[(1'R,2'R)-2'-(hydroxymethyl)cyclopropyl]oxocan-2-one；(R)-8-((1R,2R)-2-(hydroxymethyl)cyclopropyl)oxocan-2-one；(8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]oxocan-2-one
• CAS: 1029316-89-9
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: LLKQWTPMMQAMHW-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one 在 四丙基高钌酸铵 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以78%的产率得到(8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one
  参考文献：
  名称：

  茄内酯 A 和 B 的全合成

  摘要：

  介绍了茄内酯 A 和 B 的全合成。东部环丙基部分是按照非常短的化学酶促方法制备的，而西部侧链的对映选择性合成依赖于非对映异构纯硼酸烯丙酯的应用。通过应用 Nozaki-Hiyama-Kishi 反应将每个东西元素收敛后，天然产物茄内酯 A 和 B 以良好的总产率分离。

  DOI：

  10.1002/ejoc.201500700
• 作为产物：
  描述：

  1,7-庚二醇 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium chlorite 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate 、 2-iodoxybenzoic acid 、 碘苯二乙酸 、 C₁₀H₁₄*C₁₄H₁₄N₂RuS 、 hydroquinine-2,5-diphenyl-4,6-pyrimidinediyl diether 、 四丁基氟化铵 、 sodium acetate 、 三氯化硼 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 caesium carbonate 、 三乙胺 、 异丙醇 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 二甲基亚砜 、 甲苯 、 乙腈 、 oil 、 叔丁醇 为溶剂， 反应 59.5h， 生成 (8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one
  参考文献：
  名称：

  Enantioselective synthesis of cyclopropyl δ-lactonealdehydes and dodecyl-5-ene-1-yne-3-ol: advanced intermediates of solandelactone A and B

  摘要：

  A stereocontrolled synthesis of cyclopropyl delta-lactonealdehydes and dodecyl-5-ene-1-yne-3-ol is accomplished with predictable absolute stereochemistry via organocatalytic and catalytic asymmetric transfer hydrogenation reactions. The salient feature of this protocol is the genesis of chirality through an organocatalytic reaction and utilized for installing a critical bifunctional trans-cyclopropane motif, which is a key segment of every representative member of the oxylipin class of natural products such as solandelactone A and B. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.02.008

文献信息

• Total Synthesis of Solandelactones A, B, E, and F Exploiting a Tandem Petasis−Claisen Lactonization Strategy
  作者：James D. White、Christopher M. Lincoln、Jongtae Yang、William H. C. Martin、David B. Chan

  DOI：10.1021/jo800335g

  日期：2008.6.1

  Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyania-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C(22) oxylipins that parallels a hypothesis put forward previously to explain the origin of C(20) cyclopropane-containing algal products.
• Total Synthesis of Solandelactones A and B
  作者：Nils C. Eichenauer、Anja C. M. Nordschild、Martina Bischop、Dominik Schumacher、Marcel K. W. Mackwitz、Roxanne Tschersich、Thorsten Wilhelm、Jörg Pietruszka

  DOI：10.1002/ejoc.201500700

  日期：2015.9

  The total synthesis of solandelactones A and B is presented. The eastern cyclopropyl moiety was prepared following an exceptionally short chemoenzymatic approach whereas enantioselective synthesis of the western side-chain relied on the application of diastereomerically pure allyl boronates. The natural products solandelactones A and B were isolated in good overall yields following convergence of each

  介绍了茄内酯 A 和 B 的全合成。东部环丙基部分是按照非常短的化学酶促方法制备的，而西部侧链的对映选择性合成依赖于非对映异构纯硼酸烯丙酯的应用。通过应用 Nozaki-Hiyama-Kishi 反应将每个东西元素收敛后，天然产物茄内酯 A 和 B 以良好的总产率分离。
• Enantioselective synthesis of cyclopropyl δ-lactonealdehydes and dodecyl-5-ene-1-yne-3-ol: advanced intermediates of solandelactone A and B
  作者：Gullapalli Kumaraswamy、Gajula Ramakrishna、Balasubramanian Sridhar

  DOI：10.1016/j.tetlet.2011.02.008

  日期：2011.4

  A stereocontrolled synthesis of cyclopropyl delta-lactonealdehydes and dodecyl-5-ene-1-yne-3-ol is accomplished with predictable absolute stereochemistry via organocatalytic and catalytic asymmetric transfer hydrogenation reactions. The salient feature of this protocol is the genesis of chirality through an organocatalytic reaction and utilized for installing a critical bifunctional trans-cyclopropane motif, which is a key segment of every representative member of the oxylipin class of natural products such as solandelactone A and B. (C) 2011 Elsevier Ltd. All rights reserved.