constanolactone A | 130223-05-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: constanolactone A
• 英文别名: (6R)-6-[(1S,2S)-2-[(1S,2E,4S,6Z)-1,4-dihydroxydodeca-2,6-dienyl]cyclopropyl]oxan-2-one
• CAS: 130223-05-1
• 化学式: C₂₀H₃₂O₄
• 分子量: 336.472
• InChiKey: MYTQAYDWGRSARV-XPTHDSNDSA-N

物化性质

• 沸点：
  525.6±45.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2S,5R)-Menthyl chloroformate 、 constanolactone A 在 吡啶 作用下， 以 氯仿 、 甲苯 为溶剂， 反应 1.5h， 以90.4%的产率得到Bis(menthoxycarbonyl)constanolactone A
  参考文献：
  名称：

  Structure and stereochemistry of constanolactones A-G, lactonized cyclopropyl oxylipins from the red marine alga Constantinea simplex

  摘要：

  Extracts of the Oregon marine alga Constantinea simplex were found to contain a mixture of omega 6 and omega 3 unsaturated constanolactones, lactonized cyclopropyl-containing metabolites that logically derive from arachidonic and eicosapentaenoic acids, respectively. Detailed spectroscopic analysis of the isolated compounds, as natural products and various ester derivatives, afforded the planar structures of seven structurally related constanolactones. Constanolactones A-D possess 1,4-diol functionalities while constanolactones E-G contain a vicinal diol functionality. The absolute stereochemistry at all stereocenters in constanolactones A-D and at two stereocenters in constanolactones E and F were determined by chiral chromatography of fragments and chiroptical measurements of various mono- and dibenzoate derivatives and by comparable rotations within the two series (A-D and E-G). Isolation of these various diastereomeric diols, as well as of two presumed methanol adducts from CHCl3/MeOH extraction of C. simplex, leads us to speculate on the occurrence of highly unstable allylic epoxides in this red alga.

  DOI：

  10.1021/jo00103a012
• 作为产物：
  描述：

  在 chromium dichloride 、 lithium iodide 作用下， 以 乙酸乙酯 为溶剂， 反应 2.0h， 生成 constanolactone A
  参考文献：
  名称：

  手性环丙烷：constanolactones A和B的不对称合成

  摘要：

  使用新颖的立体选择性双环法制备标题海洋类二十烷酸，以产生特征性的环丙烷-δ-内酯基序。

  DOI：

  10.1016/s0040-4039(02)00699-8

文献信息

• Synthesis of solandelactone F, constanolactone A and an advanced intermediate towards solandelactone E from a common synthetic intermediate
  作者：Raju Yalla、Sadagopan Raghavan

  DOI：10.1039/c9ob00623k

  日期：——

  The stereoselective synthesis of solandelactone F, constanolactone A and an advanced intermediate towards solandelactone E, from a common synthetic intermediate, is disclosed. The propargylic sulfide stereocenter is created stereoselectively via carbon–carbon bond formation in the reaction of α-chloro sulfides with alkynylzinc reagents via 1,2-asymmetric induction by a β-siloxy group. The characteristic

  公开了从普通的合成中间体立体选择性地合成索兰内酯F，康耐醇内酯A和向索兰内酯E的高级中间体。炔丙基硫化物的立体中心是通过α-氯代硫化物与炔基锌试剂通过β-甲硅烷氧基的1,2-不对称诱导。天然产物的特征性1,4-二醇基序通过烯丙基亚砜的[2,3]σ重排或炔丙基亚砜的Mislow-Evans-Braverman重排引入，随后立体选择性还原随后的α，β引入-不饱和酮。与早期报道不同，C11 / C9甲醇中心具有出色的立体控制效果，可以轻松获得C14 / C12不同的天然产物的衍生物。催化不对称方案和底物控制的不对称诱导被用于有效引入立体异构中心。
• 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.
• Chiral cyclopropanes: asymmetric synthesis of constanolactones A and B
  作者：Jurong Yu、Jing-Yu Lai、Jianhua Ye、Narayanan Balu、L.Manmohan Reddy、Wenhu Duan、Elaine R. Fogel、Jorge H. Capdevila、J.R. Falck

  DOI：10.1016/s0040-4039(02)00699-8

  日期：2002.5

  The title marine eicosanoids were prepared using a novel, stereoselective bis-annulation to create the characteristic cyclopropane-δ-lactone motif.

  使用新颖的立体选择性双环法制备标题海洋类二十烷酸，以产生特征性的环丙烷-δ-内酯基序。
• Structure and stereochemistry of constanolactones A-G, lactonized cyclopropyl oxylipins from the red marine alga Constantinea simplex
  作者：Dale G. Nagle、William H. Gerwick

  DOI：10.1021/jo00103a012

  日期：1994.12

  Extracts of the Oregon marine alga Constantinea simplex were found to contain a mixture of omega 6 and omega 3 unsaturated constanolactones, lactonized cyclopropyl-containing metabolites that logically derive from arachidonic and eicosapentaenoic acids, respectively. Detailed spectroscopic analysis of the isolated compounds, as natural products and various ester derivatives, afforded the planar structures of seven structurally related constanolactones. Constanolactones A-D possess 1,4-diol functionalities while constanolactones E-G contain a vicinal diol functionality. The absolute stereochemistry at all stereocenters in constanolactones A-D and at two stereocenters in constanolactones E and F were determined by chiral chromatography of fragments and chiroptical measurements of various mono- and dibenzoate derivatives and by comparable rotations within the two series (A-D and E-G). Isolation of these various diastereomeric diols, as well as of two presumed methanol adducts from CHCl3/MeOH extraction of C. simplex, leads us to speculate on the occurrence of highly unstable allylic epoxides in this red alga.