(3aS,6S,6aS)-6-tetradecyltetrahydrofuro[3,4-d]oxazol-2(3H)-one | 848311-41-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (3aS,6S,6aS)-6-tetradecyltetrahydrofuro[3,4-d]oxazol-2(3H)-one
• 英文别名: (3aS,6S,6aS)-6-tetradecyl-3a,4,6,6a-tetrahydro-3H-furo[3,4-d][1,3]oxazol-2-one
• CAS: 848311-41-1
• 化学式: C₁₉H₃₅NO₃
• 分子量: 325.492
• InChiKey: DVDPRQMOYWZWGZ-BZSNNMDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  23
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aS,6S,6aS)-6-tetradecyltetrahydrofuro[3,4-d]oxazol-2(3H)-one 在 吡啶 、 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 15.0h， 生成 (2S,3S,4S)-4-acetamido-2-tetradecyltetrahydrofuran-3-yl acetate
  参考文献：
  名称：

  Enantioselective Synthesis of Pachastrissamine (Jaspin B) Using Dirhodium(II)-Catalyzed C-H Amination and Asymmetric Dihydroxylation as Key Steps

  摘要：

  通过使用Sharpless不对称二羟基化和二铑(II)催化的C-H胺化作为关键步骤，成功实现了无水植物鞘氨醇巴克斯特胺（jaspin B）的对映选择性全合成。

  DOI：

  10.1248/cpb.55.1284
• 作为产物：
  描述：

  1-十一烯 在 三乙基硅烷 、 Hoveyda-Grubbs catalyst second generation 、 三氟化硼乙醚 、 氢气 、 palladium(II) hydroxide 、 二异丁基氢化铝 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 45.5h， 生成 (3aS,6S,6aS)-6-tetradecyltetrahydrofuro[3,4-d]oxazol-2(3H)-one
  参考文献：
  名称：

  Total Synthesis of the Cytotoxic Anhydrophytosphingosine Pachastrissamine (Jaspine B)

  摘要：

  A short, 8-step synthesis of the marine natural product pachastrissamine has been developed that relies on a diastereoselective aldol reaction between a suitably protected hydantoin and an optically enriched alpha-chloroaldehyde. This synthetic route provides new opportunities for exploring structure activity relationships within this family of natural products.

  DOI：

  10.1021/jo4013223

文献信息

• Flexible and enantioselective access to jaspine B and biologically active chain-modified analogues thereof
  作者：Yahya Salma、Stéphanie Ballereau、Carine Maaliki、Sonia Ladeira、Nathalie Andrieu-Abadie、Yves Génisson

  DOI：10.1039/c004218h

  日期：——

  Whereas the all-cis tetrahydrofuran framework of the cytotoxic anhydrophytosphingosine jaspine B is considered as a relevant pharmacophore, little is known about the influence of the aliphatic chain of this amphiphilic molecule on its activity. We developed a synthetic strategy allowing flexible introduction of various lipophilic fragments in the jaspine's skeleton. The route was validated with two distinct approaches to jaspine B. Five chain-modified analogues were also prepared. Biological evaluation of these derivatives demonstrated a good correlation between their cytotoxicity and their capacity to inhibit conversion of ceramide into sphingomyelin in melanoma cells. A series of potent and selective inhibitors of sphingomyelin production was thus identified. Furthermore, the good overall potency of an ω-aminated analogue allowed us to dissociate of the pharmacological action of jaspine B from its amphiphilic nature.

  尽管细胞毒性物质anhydrophytosphingosine jaspine B的全顺式四氢呋喃骨架被认为是相关药效基团，但对于这种两亲性分子中的脂肪链对其活性的影响却知之甚少。我们开发了一种合成策略，允许在jaspine的骨架中灵活引入各种亲脂性片段。这条路线通过两种不同的方法验证了jaspine B的合成。我们还制备了五个经过链修饰的类似物。这些衍生物的生物学评价显示，它们的细胞毒性与抑制黑色素瘤细胞中神经酰胺转化为鞘磷脂的能力之间存在良好的相关性。因此，我们鉴定出一组强效且选择性的鞘磷脂生产抑制剂。此外，一个ω-氨基化类似物表现出的良好整体效能，使我们能够将jaspine B的药理作用与其两亲性本质分离。
• Stereocontrolled synthesis of cytotoxic anhydrosphingosine pachastrissamine by using [3.3] sigmatropic rearrangement of allyl cyanate
  作者：Yoshiyasu Ichikawa、Kenshi Matsunaga、Toshiya Masuda、Hiyoshizo Kotsuki、Keiji Nakano

  DOI：10.1016/j.tet.2008.09.036

  日期：2008.12

  A new route for the synthesis of the cytotoxic anhydrosphingosine pachastrissamine has been developed. [3.3] Sigmatropic rearrangement of an allyl cyanate was employed to construct the allyl amine moiety in 2 from the chiral C-4 unit 3. Oxidative cleavage of the double bond in 2, followed by THF ring formation furnished the target pachastrissamine.

  已经开发了合成细胞毒性脱水鞘氨醇pachastrissamine的新途径。[3.3]烯丙基氰酸酯的σ迁移重排用于构造烯丙基胺部分在2从手性C-4单元3。2中双键的氧化裂解，然后形成THF环，提供了目标pachastrissamine。
• Silver-Mediated exo-Selective Tandem Desilylative Bromination/Oxycyclization of Silyl-Protected Alkynes: Synthesis of 2-Bromomethylene-Tetrahydrofuran
  作者：Hyun-Ji Lee、Chaemin Lim、Soonho Hwang、Byeong-Seon Jeong、Sanghee Kim

  DOI：10.1002/asia.201100158

  日期：2011.8.1

  Three in one: The exocyclic β‐bromo enol ether is a synthetically useful functional moiety in the preparation of functionalized oxygen heterocycles. A new tandem method for the synthesis of this valuable moiety has been achieved by employing silyl‐protected acetylenic alcohols. To demonstrate the synthetic potential of the developed method, a brief total synthesis of pachastrissamine was successfully

  三合一：环外β-溴烯醇醚是制备官能化氧杂环的合成上有用的功能部分。通过使用甲硅烷基保护的炔醇，已经实现了一种新的串联方法来合成这种有价值的部分。为了证明所开发方法的合成潜力，成功尝试了简要的pachastrissamine的全合成。NBS = N-溴代琥珀酰亚胺。
• 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。
• Stereochemically Reliable Syntheses of Pachastrissamine and Its 2-epi-Congener via Oxazolidinone Precursors from an Established Starting Material N-tert-Butoxycarbonyl-Protected Phytosphingosine
  作者：Dongjoo Lee、Sanghee Kim、Hoon Bae、Hongjun Jeon、Dong Baek

  DOI：10.1055/s-0032-1317506

  日期：——

  Efficient, stereochemically unambiguous, total syntheses of pachastrissamine and its 2-epi-congener from the readily available common precursor (1R)-1-(4S,5S)-2-oxo-4-[(trityl-oxy)methyl]-1,3-oxazolidin-5-yl}pentadecyl methanesulfonate are reported. Syntheses of (3aS,6R,6aR)- and (3aS,6S,6aR)-6-tetradecy-lhexahydro-2H-cyclopenta[d][1,3]oxazol-2-one by this route have unambiguously resolved a dispute over the structures of these products.