2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(R)>-(+)-cyclopropanecarboxaldehyde | 165038-20-0

• 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: 2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(R)>-(+)-cyclopropanecarboxaldehyde
• 英文别名: (1S,2S)-2-((R)-6-oxotetrahydro-2H-pyran-2-yl)cyclopropanecarbaldehyde；(1S,2S)-2-[(2R)-6-oxooxan-2-yl]cyclopropane-1-carbaldehyde
• CAS: 165038-20-0
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: BJLRZRBGFHEVOW-GJMOJQLCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(R)>-(+)-cyclopropanecarboxaldehyde 在 chromium dichloride 、 戴斯-马丁氧化剂 、 nickel dichloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (R)-6-[(1S,2S)-2-((2E,6Z)-Dodeca-2,6-dienoyl)-cyclopropyl]-tetrahydro-pyran-2-one
  参考文献：
  名称：

  Biomimetic synthesis of a cyclopropane containing eicosanoid from the coral Plexaura homomalla. Assignment of relative configuration

  摘要：

  DOI：

  10.1021/ja00060a053
• 作为产物：
  描述：

  5-己炔酸甲酯 在 Noyori's catalyst 、 PPh₃AuCF₃COO 、 C₂₂H₃₁O₂Rh 、 cesium acetate 、 二异丁基氢化铝 、 potassium carbonate 、 三氟乙酸 、 过氧化苯甲酰 作用下， 以 四氢呋喃 、 氯仿 、 2,2,2-三氟乙醇 、 1,2-二氯乙烷 为溶剂， 反应 28.0h， 生成 2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(R)>-(+)-cyclopropanecarboxaldehyde
  参考文献：
  名称：

  手性环戊二烯基 RhIII 催化的缺电子烯烃的对映选择性环丙烷化能够快速获得 UPF-648 和 oxylipin 天然产物†

  摘要：

  手性环戊二烯基 Rh III配合物可有效催化以N-烯氧基琥珀酰亚胺为 C1 单元的缺电子烯烃的对映选择性环丙烷化反应。对于广泛的底物组合可以获得优异的不对称诱导和高非对映选择性。反应在温和条件下进行，无需采取排除空气和水的措施。此外，通过氧脂素天然产物家族成员和 KMO 抑制剂 UPF-648 的简明合成，证明了所开发方法的合成实用性。

  DOI：

  10.1039/c8sc05702h

文献信息

• Total Synthesis of Marine OxylipinsConstanolactone A and B
  作者：Jörg Pietruszka、Thorsten Wilhelm

  DOI：10.1055/s-2003-40986

  日期：——

  A short, high-yielding synthesis of the marine oxylipins constanolactoneA and B was reported. Starting from cinnamyl alcohol (3), the cylopropyl lactone moiety 2 was obtained in 28% yield (11steps). The second coupling partner, vinyl iodide 1,was isolated in 7 steps and 32% yield. Chromium mediatedaddition yielded the natural products as a 2:1 mixture (74%).

  报道了一种短小且高产率的海洋氧脂肪酸化合物constanolactone A和B的合成。从肉桂醇（3）出发，获得了环丙基内酯部分2，产率为28%（共11步）。第二个偶联伙伴，乙烯碘化物1，经过7步合成，产率为32%。铬介导的加成反应生成了自然产物的2:1混合物，产率为74%。
• Synthesis of Marine Oxylipins Constanolactones C and D
  作者：Jörg Pietruszka、Anja Rieche、Niklas Schöne

  DOI：10.1055/s-2007-986647

  日期：2007.10

  After providing the marine oxylipins constanolactones A and B, the next two members of this family were synthesized for the first time. Key to the success was a highly enantioselective and Z-selective reagent-controlled allyl addition (>99%) en route to the aliphatic side chain.

  在提供海洋oxylipins constanolactones A和B之后，该家族的下两个成员首次被合成。成功的关键是高度对映选择性和 Z 选择性试剂控制的烯丙基加成 (>99%) 到脂肪族侧链。
• Synthetic studies towards oxylipins: total synthesis of Constanolactones A and B
  作者：Catherine Barloy-Da Silva、Abdelhamid Benkouider、Patrick Pale

  DOI：10.1016/s0040-4039(00)00343-9

  日期：2000.4

  The sequential addition of functionalised chains onto a 1,2-diformylcyclopropane synthon provides rapid access to cyclopropyl oxylipins, as demonstrated here by the total synthesis of Constanolactones A–B. These eicosanoids of marine origin have been prepared in five steps, first by the regioselective γ-addition of 1-trialkylsilyloxy-1-ethoxybutadiene to (1S,2S)-1-formyl-2-(thexyldimethylsilyloxymethyl)cyclopropane

  将官能化的链顺序添加到1,2-二甲酰基环丙烷合成子上，即可快速获得环丙基氧基脂，这是通过康斯坦内酯A–B的全合成证明的。这些海洋来源的类花生酸已通过五个步骤制备，首先是将（1- S，2 S）-1-甲酰基-2-（甲氧基二甲基甲硅烷氧基甲基）环丙烷的区域选择性γ加成1-三烷基甲硅烷氧基-1-乙氧基丁二烯。官能团修饰，添加（1 E，3 S，5 Z）-3-羟基不饱和烯-1,5-二烯基有机金属。
• Cyclopropane-Containing Eicosanoids of Marine Origin. Biomimetic Synthesis of Constanolactones A and B from the Alga Constantinea simplex
  作者：James D. White、Mark S. Jensen

  DOI：10.1021/ja00128a008

  日期：1995.6

  Asymmetric syntheses of 7, a substance isolated from incubation of arachidonic acid with an acetone powder of the coral Plexaura homomalla, and of constanolactones A (9) and B (10), metabolites of the red alga Constantinea simplex, are described. The key step involves stannic chloride-mediated cyclization of the oxirane derived from Sharpless epoxidation of 10-hydroxy-5,8-decadienoates, and is shown to yield a trans disubstituted cyclopropane Linked to a delta-lactone. Both (R) and (S) configurations at C5 of the lactone are produced in the cyclization, the ratio being independent of olefin geometry in the acyclic precursor, Elaboration of the cyclization products via Nozaki-Kishi coupling of the derived aldehydes 26 and 37 with the appropriate (1E,5Z)-1-iodo-1,5-undecadiene led to 7, 9, and 10, thereby establishing the relative configuration of 7 and confirming the absolute configuration of 9 and 10.
• 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.