(8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one | 1029316-90-2

• 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: (1R,2R)-2-[(R)-8'-oxooxocan-2'-yl]cyclopropanecarbaldehyde；(1R,2R)-2-((R)-8-oxooxocan-2-yl)cyclopropanecarbaldehyde；(1R,2R)-2-[(2R)-8-oxooxocan-2-yl]cyclopropane-1-carbaldehyde
• CAS: 1029316-90-2
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: WEEAIGWHUIDHHF-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 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 、 dimethyl (S,Z)-(3-((tert-butyldimethylsilyl)oxy)-2-oxoundec-5-en-1-yl)phosphonate 在 caesium carbonate 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 96.0h， 以64%的产率得到
  参考文献：
  名称：

  Solandelactone I的全合成

  摘要：

  由于海洋天然产物solandelactones A-I是从分离水螅Solanderia塞康达和由Seo等人调查。在1996年，人们对这些海洋上的脂蛋白进行了大量的合成研究。然而，苏糖内酯I的结构解析仍然不完全，并且没有合成的报道。在我们的逆合成分析的基础上，所述键积木合并在Horner-Wadsworth-Emmons反应，为所有四个非对映体的合成stereodivergent创建两个共同中间体1 - 4匹配solandelactone I.公布的比较的所提出的结构天然产物solandelactone I的分析数据以及从合成方法中获得的非对映异构体数据1– 4启用了异构体3的结构分配；拟议的海洋氧化脂生物合成途径也支持该结果。

  DOI：

  10.1021/acs.jnatprod.5b00757
• 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 、 四丙基高钌酸铵 、 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 、 N-甲基吗啉氧化物 、 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 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。
• Total Synthesis of Marine Oxylipins Solandelactones A-H
  作者：Jörg Pietruszka、Anja C. M. Rieche

  DOI：10.1002/adsc.200800198

  日期：2008.6.9

  The Solandelactones A–H have been synthesized via a short convergent approach utilizing common building blocks. Based on the diastereoselectivity of the crucial final addition step and on the comparison of prominent NMR data, a structural revision was necessary.

  Solandelactones A–H通过使用通用构件的短时收敛方法合成。基于关键的最终加成步骤的非对映选择性，以及对著名的NMR数据进行比较，有必要对结构进行修订。
• Stereocontrolled asymmetric synthesis of syn-E-1,4-diol-2-enes using allyl boronates and its application in the total synthesis of solandelactone F
  作者：Anna Robinson、Varinder K. Aggarwal

  DOI：10.1039/c2ob06975j

  日期：——

  The solandelactones A–H comprise a novel class of oxygenated fatty acids bearing an eight-membered lactone, transcyclopropane, and a 2-ene-1,4-diol subunit. The relative stereochemistry of the 1,4-diol subunit is anti in solandelactones A, C, E & G, and syn in solandelactones B, D, F & H. Having prepared one member of the solandelactones bearing anti stereochemistry (solandelactone E), we have targeted the syn series and developed methodology for the synthesis of enantioenriched syn-2-ene-1,4-diols. The methodology comprises asymmetric deprotonation of an alkyl 2,4,6-triisopropylbenzoate using sBuLi/sparteine, followed by addition of the α-lithiobenzoate to β-silyl vinyl boronic acid ethylene glycol ester. The boron-ate complex generated undergoes a 1,2-metallate rearrangement furnishing an intermediate allyl boronic ester which is trapped by an aldehyde in the presence of MgBr2 to furnish anti-β-hydroxyE-allylsilanes in good yields, high diastereoselectivity and high enantioselectivity. These sensitive products were oxidized using mCPBA to the corresponding epoxides and subsequently treated with acid to furnish syn-E-2-ene-1,4-diols (∼4 : 1 d.r.). Application of the methodology to appropriately functionalized aldehyde and ω-alkenyl 2,4,6-triisopropylbenzoate coupling partners, led to a short, highly selective route to solandelactone F (bearing a syn-E-2-ene-1,4-diol).

  Solandelactones A-H是一类新颖的含氧脂肪酸，具有八元内酯、反式环丙烷和2-烯-1,4-二醇子单元。在solandelactones A、C、E和G中，1,4-二醇子单元的相对立体化学为反式，而在solandelactones B、D、F和H中为顺式。我们已合成了具有反式立体化学的solandelactone E，并针对顺式系列开展研究，开发了合成富含对映体的顺式2-烯-1,4-二醇的方法。这一方法包括使用sBuLi/sparteine进行烷基2,4,6-三异丙基苯甲酸酯的非对称去质子化，随后将α-锂苯甲酸酯加入到β-硅基乙烯基硼酸乙二醇酯中。生成的硼酸盐复合物经历1,2-金属化重排，生成中间体烯丙基硼酸酯，在MgBr2存在下与醛反应，产生高产率、高立体选择性和高对映选择性的反式β-羟基E-烯丙基硅烷。这些敏感产物使用mCPBA被氧化为相应的环氧化物，并随后用酸处理生成顺式E-2-烯-1,4-二醇（约4:1的双对映体比）。将该方法应用于适当官能化的醛和ω-烯烃-2,4,6-三异丙基苯甲酸酯的偶联反应，得到了通向solandelactone F（具有顺式E-2-烯-1,4-二醇）的一条简短且高选择性路线。
• 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.
• 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.