(5R,7R)-5,7-dihydroxy-1-(4-hydroxyphenyl)icosan-3-one | 945736-74-3

• 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: (5R,7R)-5,7-dihydroxy-1-(4-hydroxyphenyl)icosan-3-one
• CAS: 945736-74-3
• 化学式: C₂₆H₄₄O₄
• 分子量: 420.633
• InChiKey: YDJZXYKBDQEICO-AOYPEHQESA-N

物化性质

• 沸点：
  595.0±40.0 °C(predicted)
• 密度：
  1.024±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  30
• 可旋转键数：
  19
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5R,7R)-5,7-dihydroxy-1-(4-hydroxyphenyl)icosan-3-one 在 [双(三氟乙酰氧基)碘]苯 作用下， 以 水 、 丙酮 为溶剂， 反应 16.25h， 生成 aculeatin A
  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
• 作为产物：
  描述：

  (5R,7R)-5,7-bis{[(tert-butyl)(dimethyl)silyl]oxy}-1-(4-hydroxyphenyl)icosan-3-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 (5R,7R)-5,7-dihydroxy-1-(4-hydroxyphenyl)icosan-3-one
  参考文献：
  名称：

  Prins环化立体选择性合成Aculeatin A和B

  摘要：

  描述了aculeatins A和B的总合成，证明了Prins环化在天然产物合成中的多功能性。该方法是收敛的且高度立体选择性的。将吗啉酰胺与炔烃偶联和PIFA介导的氧化螺环化用作关键步骤。 aculeatins-Prins环化-吗啉酰胺-PIFA介导的氧化螺环化

  DOI：

  10.1055/s-0029-1217144

文献信息

• Total synthesis of aculeatins A and B via a tethered oxa-Michael approach
  作者：S. Chandrasekhar、Ch. Rambabu、T. Shyamsunder

  DOI：10.1016/j.tetlet.2007.05.026

  日期：2007.7

  A stereocontrolled total synthesis of aculeatins A and B has been achieved in eight steps and in 15% overall yield. The key feature of this synthetic approach is the application of a Marouka allylation and tethered intramolecular oxa-Michael reaction to install the required stereocentres on the tetrahydropyran ring.

  通过八个步骤实现了立体式Aculeatins A和B的总合成，总收率为15％。这种合成方法的关键特征是应用了Marouka烯丙基化和分子内氧杂-迈克尔基化反应，将所需的立体中心安装在四氢吡喃环上。
• Total Synthesis of Aculeatins A and B from L-Malic Acid
  作者：Jhillu S. Yadav、Yerragorla Gopala Rao、Dandekar Chandrakanth、Kontham Ravindar、Basi V. Subba Reddy

  DOI：10.1002/hlca.201000084

  日期：2010.12

  moiety with appropriate configuration was accomplished from the commercially available L‐malic acid. The key steps in this synthesis are the Barbier allylation, LiAlH4/LiI‐mediated syn‐stereoselective 1,3‐asymmetric reduction, and phenyliodine bis(trifluoroacetate) (=[bis(trifluoroacetoxy)iodo]benzene; PIFA) mediated oxidative spirocyclization.

  描述了细胞毒性螺酮天然产物aculeatin A和B的有效全合成。具有适当构型的1,3,5-三醇部分的合成是通过市售的L-苹果酸完成的。在该合成中的关键步骤是Barbier的烯丙基化，的LiAlH 4 /的LiI介导顺-stereoselective 1,3-不对称还原，和phenyliodine双（三氟乙酸盐）（= [双（三氟乙酰氧基）碘]苯; PIFA）介导的氧化螺环化。
• A modular total synthesis of aculeatins A, B, E, F and 6-epi-aculeatins E, F
  作者：C.V. Ramana、Sunil Kumar Pandey

  DOI：10.1016/j.tet.2009.10.058

  日期：2010.1

  The total synthesis of aculeatins A, B, E and F confirming the assigned absolute configuration of recently isolated aculeatins E and F is documented. A convergent approach has been designed by the addition of both the terminal units (phenol and side chain) at an advanced stage. The central 1,3,5-triol unit with the requisite stereochemistry was prepared from the commercially available α-d-glucoheptonic-γ-lactone

  记录了aculeatins A，B，E和F的总合成，证实了最近分离出的aculeatins E和F的指定绝对构型。通过在高级阶段同时添加两个末端单元（苯酚和侧链），已设计出一种收敛方法。由市售的α - d-葡庚七酮-γ-内酯制备具有必要立体化学的中心1,3,5-三醇单元。二炔中间体的氢解过程中的选择性O-脱苄基反应以及伴随螺环化的一锅酚氧化反应突出了已完成的总合成过程。
• The Stereoselective Total Synthesis of Aculeatin A and B via Prins Cyclization
  作者：J. Yadav、N. Thrimurtulu、M. Venkatesh、A. Prasad

  DOI：10.1055/s-0029-1217144

  日期：2010.2

  The total synthesis of aculeatins A and B is described proving the versatility of Prins cyclization in natural product synthesis. The approach is convergent and highly stereoselective. Morpholine amide coupling with an alkyne and PIFA-mediated oxidative spirocyclization were utilized as key steps. aculeatins - Prins cyclization - morpholine amide - PIFA-mediated oxidative spirocyclization

  描述了aculeatins A和B的总合成，证明了Prins环化在天然产物合成中的多功能性。该方法是收敛的且高度立体选择性的。将吗啉酰胺与炔烃偶联和PIFA介导的氧化螺环化用作关键步骤。 aculeatins-Prins环化-吗啉酰胺-PIFA介导的氧化螺环化
• Diastereodivergent Strategies for the Synthesis of Homochiral Aculeatins
  作者：Marine Peuchmaur、Yung-Sing Wong

  DOI：10.1021/jo0707986

  日期：2007.7.1

  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.