(+/-)-dihydromahubanolide B | 71325-97-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (+/-)-dihydromahubanolide B
• 英文别名: (3Z,4S,5S)-3-hexadecylidene-4-hydroxy-5-methyloxolan-2-one
• CAS: 71325-97-8；71358-20-8；71358-21-9；71359-04-1；71359-05-2；78339-87-4；78339-88-5；78339-89-6；84845-73-8；121703-31-9
• 化学式: C₂₁H₃₈O₃
• 分子量: 338.531
• InChiKey: LAJHPFCGLXGQIB-NUFQYXKXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  24
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  十六醛 在 AD-mix-α 、 甲基磺酰胺 、 三苯基膦 、 lithium diisopropyl amide 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 102.0h， 生成 (+/-)-dihydromahubanolide B
  参考文献：
  名称：

  Stereopure 1,3-butadiene-2-carboxylates and their conversion into non-racemic α-alkylidenebutyrolactone natural products by asymmetric dihydroxylation

  摘要：

  Dienoic esters 1 with the four possible permutations of the C=C configurations were prepared in two steps via non-stereoselective aldol additions followed by stereospecific beta -eliminations. Sharpless dihydroxylations of these esters yielded natural and unnatural alpha -alkylidene-beta -hydroxybutyrolactones 2. Among these were synthetic dihydromahubanolide B (cis,Z-2a), isodihydromahubanolide B (cis,E-2a) and, for the first time, litsenolide D-1 (ent-trans,Z-2b) and the enantiomer trans,E-2b of litsenolide D-2. Competitively, dihydroxyesters 10 were formed. (C) 2001 Elsevier Science Ltd. Al rights reserved.

  DOI：

  10.1016/s0040-4039(01)00598-6

文献信息

• SYNTHESIS OF (−)-DIHYDROMAHUBANOLIDE B AND (−)-ISODIHYDROMAHUBANOLIDE B
  作者：Akira Tanaka、Kyohei Yamashita

  DOI：10.1246/cl.1981.319

  日期：1981.3.5

  The total synthesis of (−)-dihydromahubanolide B and (−)-isodihydromahubanolide B isolated from the Amazonian Lauraceae Licariamahuba (Samp.) Kosterm was achieved starting from (−)-methyl 5-hydroxy methyl -2,2-dimethyl-1,3-dioxolane-4-carboxylate which was readily available from L-(+)-tartaric acid.

  (-)-5-羟基甲基-2,2-二甲基-1,3-二氧戊环-4-羧酸甲酯为起点，实现了从亚马逊月桂科植物 Licariamahuba (Samp.) Kosterm 分离出的(-)-二氢阿胡巴内酯 B 和(-)-异二氢阿胡巴内酯 B 的全合成。
• The synthesis of the dihydromahubanolides
  作者：William W. Wood、Graham M. Watson

  DOI：10.1039/p19900003201

  日期：——

  Two epimeric, naturally occurring α-alkylidene-γ-butyrolactones have been prepared from a carbohydrate precursor, using a Wittig reaction to form an exocyclic double bond either with or without epimerisation at the centre α to the olefin, depending on the reaction conditions employed.

  根据所采用的反应条件，使用维特希（Wittig）反应在烯烃的中心α上带有或不带有差向异构体的情况下，通过维蒂希反应形成了环外双键，由碳水化合物前体制备了两种天然存在的差向异构体，即α-亚烷基-γ-丁内酯。
• (<i>Z</i>)-3-Alkylidene-4,5-dihydro-4-hydroxy-5-methyl-2-(3<i>H</i>)-furanones by Regio- and Diastereo-selective Ene Reaction of Singlet Oxygen (Schenk Reaktion) with γ-Hydroxy Vinylstannanes: An Enantioselective Synthesis of Dihydromahubanolide B
  作者：Waldemar Adam、Peter Klug

  DOI：10.1055/s-1994-25525

  日期：——

  (Z)-3-Alkylidene-4,5-dihydro-4-hydroxy-5-methyl-2-(3H)-furanones 5 were prepared from appropriately substituted propargylic alcohols 1 by a sequence of hydromagnesation to γ-hydroxy vinylstannanes 2, subsequent photooxygenation and reduction to stannyl diols 3, iododestannylation to iodo diols 4, and finally cyclization by palladium-catalyzed carbonylation (for 5a) or Ni(CO)2(PPh3)2 (for 5b,c). The reaction sequence can be performed enantioselectively by starting with chiral propargylic alcohols. The current approach constitutes a convenient four-step synthesis of optically active lactones 5 from readily available starting materials and is applied herein to the preparation of the natural lactone dihydromahubanolide B.

  (Z)-3-亚烷基-4,5-二氢-4-羟基-5-甲基-2-(3H)-呋喃酮 5 由适当取代的炔丙醇 1 通过一系列水镁化制备 γ-羟基乙烯基锡烷 2，随后光氧化和还原为甲锡烷基二醇 3，碘脱甲烷基化为碘二醇 4，最后通过钯催化的羰基化（对于 5a）或 Ni(CO)2(PPh3)2（对于 5b,c）进行环化。该反应顺序可以通过从手性炔丙醇开始对映选择性地进行。目前的方法由容易获得的起始材料构成光学活性内酯5的方便的四步合成，并且在本文中应用于天然内酯二氢mahubanolide B的制备。
• Total synthesis of Lauraceae lactones: obtusilactones, litsenolides, and mahubanolides
  作者：Susan Wells Rollinson、Richard A. Amos、John A. Katzenellenbogen

  DOI：10.1021/ja00404a023

  日期：1981.7
• Stereoelectronic Control of the Diastereoselectivity in the Photooxygenation (Schenck Ene Reaction) of an Electron-Poor Allylic Alcohol and Its Ethers
  作者：Waldemar Adam、Jürgen Renze、Thomas Wirth

  DOI：10.1021/jo971963s

  日期：1998.1.1