(2R,4S,6S)-4-hydroxy-2-tridecyl-1,7-dioxadispiro[5.1.5.2]pentadeca-9,12-dien-11-one | 849925-13-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,4S,6S)-4-hydroxy-2-tridecyl-1,7-dioxadispiro[5.1.5.2]pentadeca-9,12-dien-11-one
• 英文别名: 6-epi-aculeatin D；(+)-aculeatin D；aculeatin D；(-)-aculeatin A；(2S,4R,6S)-2-hydroxy-4-tridecyl-5,7-dioxadispiro[5.1.58.26]pentadeca-9,12-dien-11-one
• CAS: 849925-13-9
• 化学式: C₂₆H₄₂O₄
• 分子量: 418.617
• InChiKey: UAFRNLHPKTXIOW-GSLIJJQTSA-N

物化性质

• 沸点：
  575.1±50.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  30
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (2S,4S,6R)-2-[2-(4-hydroxyphenyl)ethyl]-6-tridecyltetrahydropyran-2,4-diol 在 [双(三氟乙酰氧基)碘]苯 作用下， 以 水 、 丙酮 为溶剂， 反应 5.25h， 生成 (2R,4S,6S)-4-hydroxy-2-tridecyl-1,7-dioxadispiro[5.1.5.2]pentadeca-9,12-dien-11-one
  参考文献：
  名称：

  Diastereodivergent Strategies for the Synthesis of Homochiral Aculeatins

  摘要：

  We report concise and stereocontrolled syntheses of aculeatins (-)-A, (+)-B, (+)-D, and (+)-6-epi-D. Diastereodivergent 1,3-inductions in Mukaiyama aldol coupling contribute to reduce steps and to increase flexibility with reactants having sterically restricted proximal substituents (i.e., CH2), involving either a good anti or a moderate syn 1,3-induction, depending on the nature of protecting group (P). In addition, the 3,5-syn-diol-ketone resulting from concomitant deprotection of the beta-alkoxy (Tr = trityl) group proves to be remarkably stable whereas the 3,5-anti diastereoisomer cyclizes spontaneously to the corresponding tetrahydropyran hemiketal, thus enabling a useful and facile separation. The second part of our study is devoted to improving the yield and the diastereoselectivity of the final phenolic oxidation reaction leading to aculeatins.

  DOI：

  10.1021/jo0707986

文献信息

• Total Synthesis of Aculeatins A, B and D and 6-epi-Aculeatin D via an Asymmetric­ Aldol Approach
  作者：Biswanath Das、Lingaiah Maram

  DOI：10.1055/s-0033-1340866

  日期：——

  Abstract Simple and efficient stereoselective total syntheses of aculeatins A, B and D and 6-epi-aculeatin D starting from 1-tetradecanal have been accomplished. The synthesis is based on the Crimmins aldol reaction involving a chiral auxiliary. Simple and efficient stereoselective total syntheses of aculeatins A, B and D and 6-epi-aculeatin D starting from 1-tetradecanal have been accomplished. The

  摘要 从1-四癸醛开始的aculeatins A，B和D和6- epi - aculeatin D的简单，有效的立体选择性总合成已经完成。该合成基于涉及手性助剂的Crimmins aldol反应。 从1-四癸醛开始的aculeatins A，B和D和6- epi - aculeatin D的简单，有效的立体选择性总合成已经完成。该合成基于涉及手性助剂的Crimmins aldol反应。
• Total Synthesis of (+)-Aculeatin D and (+)-6-epi-Aculeatin D
  作者：J. Yadav、K. Rao、K. Ravindar、B. Reddy

  DOI：10.1055/s-0029-1218546

  日期：2010.1

  synthesis of spiroketal natural product (+)-aculeatin D and unnatural (+)-6-epi-aculeatin D has been accomplished. Sharpless kinetic resolution of secondary allylic alcohol and phenyliodine(III) bis(trifluoroacetate) (PIFA)-mediated oxidative spirocyclization were used as key steps in this synthesis.

  螺缩酮天然产物(+)-aculeatin D和非天然(+)-6-ePI-aculeatin D的立体选择性全合成已经完成。仲烯丙醇和苯基碘 (III) 双（三氟乙酸酯）（PIFA）介导的氧化螺环化的 Sharpless 动力学拆分被用作该合成的关键步骤。
• Enantioselective synthesis and absolute configurations of aculeatins A, B, D, and 6-epi-aculeatin D
  作者：Paula Álvarez-Bercedo、Eva Falomir、Miguel Carda、J.A. Marco

  DOI：10.1016/j.tet.2006.07.076

  日期：2006.10

  The three naturally occurring, bioactive spiroacetals aculeatins A, B, and D, as well as the non-natural 6-epi-aculeatin D have been synthesized for the first time in enantiopure form using an asymmetric allylation as the only chirality source. A further key step was a stereoselective aldol reaction with remote induction. The absolute configurations of the natural products have been established and

  使用不对称烯丙基化作为唯一手性来源，首次以对映纯形式合成了三种天然存在的，具有生物活性的螺缩醛aculeatins A，B和D以及非天然的6- epi -aculeatinD 。另一个关键步骤是具有远程感应的立体选择性醛醇缩合反应。已经确定了天然产物的绝对构型，并且纠正了错误的结构分配。
• A Chiron Approach to the Total Synthesis of (+)-Aculeatin D
  作者：Zhi-Bin Zhen、Jian Gao、Yikang Wu

  DOI：10.1021/jo801296x

  日期：2008.9.19

  A synthesis of natural aculeatin D has been achieved, with the key stereogenic centers taken from inexpensive and readily available D-xylose. In elaboration of D-xylose into a desired form readily applicable in synthesis a previously misinterpreted and overlooked abnormal selectivity in hydroxyl protection was noticed and exploited. Protocols were developed for monotosylation of a triol insoluble in

  已经实现了天然针叶苷D的合成，其中关键的立体异构中心取自廉价且容易获得的D-木糖。在将D-木糖精加工成易于适用于合成的所需形式时，注意到并利用了先前被误解和忽视的羟基保护的异常选择性。已开发出分别在PIFA介导的氧化螺环化反应中不溶于CH2Cl2的三醇单甲苯基化和“冻结”不太稳定的异构体（aculeatin D）的方案。还解决了文献中热力学上更稳定的二噻吩碳负离子在苄基保护基上的无法解释的去质子化。
• Polyol Synthesis with β-Oxyanionic Alkyllithium Reagents: Syntheses of Aculeatins A, B, and D
  作者：Viengkham Malathong、Scott D. Rychnovsky

  DOI：10.1021/ol901623h

  日期：2009.9.17

  route was developed. The β-phenylthio alcohols were prepared from optically pure oxiranes. Deprotonation and reductive lithiation generated the key intermediate, a β-oxyanionic alkyllithium reagent. Addition to a Weinreb amide produced the β-hydroxy ketone in >90% yield using only 1.5 equiv of the phenylthio alcohol. Stereoselective reduction of the ketone led to either the syn- or anti-1,3-diol. This simple

  开发了使用非羟醛路线合成酮羟醛产品。β-苯硫醇由光学纯环氧乙烷制备。去质子化和还原锂化产生了关键中间体，β-氧阴离子烷基锂试剂。添加到 Weinreb 酰胺中，仅使用 1.5 当量的苯硫醇即可以 >90% 的收率产生 β-羟基酮。酮的立体选择性还原导致合成-或反-1,3-二醇。这个简单的收敛序列用于从一个常见的中间体制备 aculeatins A、B 和 D。