ent-jaspine B | 923287-02-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: ent-jaspine B
• 英文别名: (2R,3R,4R)-4-Amino-2-tetradecyloxolan-3-OL
• CAS: 923287-02-9
• 化学式: C₁₈H₃₇NO₂
• 分子量: 299.497
• InChiKey: FBQCDJRSCUVUFL-KZNAEPCWSA-N

物化性质

• 熔点：
  91-93 °C
• 沸点：
  422.9±45.0 °C(Predicted)
• 密度：
  0.935±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  21
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ent-jaspine B 、 乙酸酐 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以0.08 g的产率得到(2R,3R,4R)-4-acetamido-2-tetradecyltetrahydrofuran-3-yl acetate
  参考文献：
  名称：

  Total synthesis of the acetyl derivatives of lyxo-(2R,3R,4R)-phytosphingosine and (−)-jaspine B

  摘要：

  The total synthesis of acetyl derivatives of lyxo-(2R,3R,4R)-phytosphingosine and (-)-jaspine B using a Grignard reaction on sugar-imine and a Wittig reaction as the key steps. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.04.009
• 作为产物：
  描述：

  (R)-benzyl 2-((5R,6R)-2,2,3,3,8,8,9,9-octamethyl-6-vinyl-4,7-dioxa-3,8-disiladecan-5-yl)aziridine-1-carboxylate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium on activated carbon 、 氢氟酸 、 氢气 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 35.0h， 生成 ent-jaspine B
  参考文献：
  名称：

  Formation of tetrahydrofurans via a 5-endo-tet cyclization of aziridines – synthesis of (−)-pachastrissamine

  摘要：

  据报道，2-羟基烷基环氧乙烷或氮丙啶可以形成四氢呋喃。在温和条件下，氮丙啶的5-endo-tet环化/开环反应顺利进行，生成四氢呋喃（THFs）。相比之下，环氧乙烷的相应过程未能成功，需要通过一系列SN2取代/环化步骤才能形成THFs。本文描述了该过程在制备ent-(−)-pachastrissamine中的应用。

  DOI：

  10.1039/c3ob40797g

文献信息

• Stereodivergent synthesis of jaspine B and its isomers using a carbohydrate-derived alkoxyallene as C₃-building block
  作者：Volker Martin Schmiedel、Stefano Stefani、Hans-Ulrich Reissig

  DOI：10.3762/bjoc.9.291

  日期：——

  Herein we present the synthesis of the anhydrophytosphingosine jaspine B and three of its stereoisomers using a carbohydrate-derived alkoxyallene in order to obtain the products in enantiopure form. Key step of the reaction sequence is the addition of the lithiated alkoxyallene to pentadecanal, setting the configuration at the later C-2 of the ring system. This reaction step proceeds with moderate

  在此，我们介绍了使用碳水化合物衍生的烷氧基丙二烯合成脱水植物鞘氨醇 jaspine B 及其三种立体异构体，以获得对映体纯形式的产物。反应序列的关键步骤是将锂化的烷氧基丙二烯加成到十五烷醛，在环系统的后面 C-2 处设置构型。该反应步骤以中等选择性进行，因此导致对天然产物及其对映体的立体发散方法。金催化的 5-内环化得到相应的二氢呋喃，经过分离、烯醇醚部分的叠氮化和两个随后的还原步骤，得到天然产物及其立体异构体。
• Rapid access to jaspine B and its enantiomer
  作者：Cécile Santos、Isabelle Fabing、Nathalie Saffon、Stéphanie Ballereau、Yves Génisson

  DOI：10.1016/j.tet.2013.06.091

  日期：2013.9

  reported. This synthesis relies on a one pot regioselective aziridine ring-opening followed by intramolecular cyclization to install the cis-amino–alcohol pattern of jaspine B and on a modified Julia olefination of the lactone followed by a diastereoselective hydrogenation for the introduction of the C14 aliphatic chain. The separation of enantiomers in the course of this synthesis was achieved by

  到jaspine B及其对映体A的快速访问ENT被报告从2,3-氮丙啶基-γ内酯-jaspine乙。这种合成依赖于一锅区域选择性氮丙啶开环，然后进行分子内环化，以安装茉莉花B的顺式-氨基-醇型；内酯经修饰的Julia烯化，然后通过非对映选择性氢化引入C14脂族链。在该合成过程中对映异构体的分离通过超临界流体色谱法实现。评价了两种对映异构体的细胞毒性。
• Total synthesis of pachastrissamine (jaspine B) enantiomers from d-glucose
  作者：C.V. Ramana、Awadut G. Giri、Sharad B. Suryawanshi、Rajesh G. Gonnade

  DOI：10.1016/j.tetlet.2006.11.048

  日期：2007.1

  Synthesis of both enantiomers of pachastrissamine is described from a common chiral template. The stereoselective construction of the central tetrahydrofuran units was based on the pseudodesymmetrization of a pentodialdo-1,4-furanose derivative taking advantage of the latent symmetry present. (c) 2006 Published by Elsevier Ltd.
• Pachastrissamine (jaspine B) and its stereoisomers inhibit sphingosine kinases and atypical protein kinase C
  作者：Yuji Yoshimitsu、Shinya Oishi、Jun Miyagaki、Shinsuke Inuki、Hiroaki Ohno、Nobutaka Fujii

  DOI：10.1016/j.bmc.2011.07.061

  日期：2011.9

  Sphingosine kinases (SphKs) are oncogenic enzymes that regulate the critical balance between ceramide and sphingosine-1-phosphate. Much effort has been dedicated to develop inhibitors against these enzymes. Naturally occurring pachastrissamine (jaspine B) and all its stereoisomers were prepared and evaluated for their inhibitory effects against SphKs. All eight stereoisomers exhibited moderate to potent inhibitory activity against SphK1 and SphK2. Inhibitory effects were profiled against protein kinase C (PKC) isoforms by in vitro experiments. Atypical PKCs (PKC zeta and PKC iota) were inhibited by several pachastrissamine stereoisomers. The improved activity over N,N-dimethylsphingosine suggests that the cyclic scaffold in pachastrissamines facilitates potential favorable interactions with SphKs and PKCs. (C) 2011 Elsevier Ltd. All rights reserved.
• Formation of tetrahydrofurans via a 5-endo-tet cyclization of aziridines – synthesis of (−)-pachastrissamine
  作者：Chen-Wei Lin、Sin-Wei Liu、Duen-Ren Hou

  DOI：10.1039/c3ob40797g

  日期：——

  The formation of tetrahydrofurans from 2-hydroxyalkyl-oxirane or aziridine is reported. The 5-endo-tet cyclization/ring opening of aziridine proceeded smoothly to give tetrahydrofurans (THFs) under mild conditions. In contrast, the corresponding process of oxirane was unsuccessful and a sequence of SN2 substitution/cyclization was required to form THFs. The application of the process to prepare ent-(−)-pachastrissamine is described.

  据报道，2-羟基烷基环氧乙烷或氮丙啶可以形成四氢呋喃。在温和条件下，氮丙啶的5-endo-tet环化/开环反应顺利进行，生成四氢呋喃（THFs）。相比之下，环氧乙烷的相应过程未能成功，需要通过一系列SN2取代/环化步骤才能形成THFs。本文描述了该过程在制备ent-(−)-pachastrissamine中的应用。