trans-(+)-laurediol | 37866-22-1

• 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: trans-(+)-laurediol
• 英文别名: (3E,6R,7R,9Z,12E)-pentadeca-3,9,12-trien-1-yne-6,7-diol
• CAS: 37866-22-1
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: IAEFGPNTEIJHNJ-BOUWRWNBSA-N

物化性质

• 沸点：
  371.9±42.0 °C(predicted)
• 密度：
  0.990±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-(+)-laurediol 在 叔丁基过氧化氢 、 (ethyl)[cis-(piperidine-2,6-diyl)dimethyl]vanadate 作用下， 以 正壬烷 、 氯仿 为溶剂， 反应 24.0h， 以37%的产率得到(2R,3R,5R)-5-[(1R,3E)-1-hydroxyhex-3-enyl]-2-[(2E)-pent-2-en-4-yneyl]tetrahydrofuran-3-ol
  参考文献：
  名称：

  Activating tert-butyl hydroperoxide by chelated vanadates for stereoselectively preparing sidechain-functionalized tetrahydrofurans

  摘要：

  tert-Butyl hydroperoxide (TBHP) stereoselectively oxidizes substituted 4-pentenols, when activated by (ethyl)[cis-(piperidine-2,6-diyl)dimethyl] vanadates. The reaction affords (tetrahydrofuran-2-yl)methanols in up to 89% yield, and in stereoselectivity ranging between moderate (cis:trans = 32:68) to excellent (>99:1). Correlating structures of 4-pentenols, differing by substitution at tetragonal and trigonal stereocenters, to configuration of products obtained from oxidative cyclization provides a reaction model explaining the origin of stereoselectivity by (i) intramolecular oxygen atom transfer to (ii) a chair-like folded alkenol, being (iii) hydrogen-bonded to one of the two aminodiolate oxygens of the chelated vanadate, having (iv) substituents in the chair-like transition structure preferentially aligned equatorially. Substituents at trigonal stereocenters improve 2,5-cis- and 2,4-trans-selectivity for oxidative 4-pentenol cyclization in case of (Z)-configuration. An (E)-substituent does not alter selectivity exerted by a terminal (Z)-substituent of similar steric size. Larger (E)-groups increase the fraction of 2,5-trans-cyclized products. The reaction model additionally implements results from vanadium-51 NMR spectroscopy and density functional theory. According to theory, the (dialkoxy)(oxo)vanadium substituent exerts in the preferred end-on conformation almost no effect on structure and bonding of the peroxide group in tert-butylperoxy vanadates. Changing conformation to a higher in energy side-on arrangement puts the vanadate-bound tert-butylperoxy group into a position to serve in a concerted reaction as combined electron acceptor and oxygen atom donor. (C) 2015 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jinorgbio.2015.04.009
• 作为产物：
  描述：

  反式-3-己烯-1-醇 在 咪唑 、 4 Angstroem MS 、 potassium tert-butylate 、 四丁基氟化铵 、 碘 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 乙腈 、 苯 为溶剂， 反应 8.08h， 生成 trans-(+)-laurediol
  参考文献：
  名称：

  反式-（+）-月桂二醇的短合成

  摘要：

  提出了一种高度收敛和短合成的反式-（+）-月桂二醇。该合成具有通过β，γ-不饱和酯的Sharpless AD反应高效地构建顺式3-羟基-γ-丁内酯的特征。

  DOI：

  10.1016/s0040-4039(00)00190-8

文献信息

• Enzymatic Bromo-ether Cyclization of Laurediols with Bromoperoxidase
  作者：Akio Fukuzawa、Mya Aye、Yasunori Takasugi、Masao Nakamura、Mamoru Tamura、Akio Murai

  DOI：10.1246/cl.1994.2307

  日期：1994.12

  Natural (3E,6R,7R)- and (3Z,6S,7S)-laurediols were subjected to enzymatic reaction with the partially purified bromoperoxidase from the red alga, Laurencia nipponica, in the presence of H2O2 and NaBr to afford laurencin and prelaureatin, respectively. The further reaction of these products with bromoperoxidase gave rise to the bicyclic bromo-ethers.

  天然(3E,6R,7R)-和(3Z,6S,7S)-月桂醇在 H2O2 和 NaBr 的作用下，与部分纯化的红藻月桂过氧化物酶发生酶促反应，分别生成月桂苷和前月桂苷。这些产物与溴过氧化物酶的进一步反应生成了双环溴醚。
• Enantiomeric syntheses of 6(R), 7(R) and 6(S), 7(S) trans- and cis-laurediol
  作者：B Añorbe、V.S Martín、J.M Palazón、J.M Trujillo

  DOI：10.1016/s0040-4039(00)85115-1

  日期：1986.1
• Efficient syntheses of trans-(+)-laurediol from carbohydrate precursors
  作者：Rajendrakumar Reddy Gadikota、Adam I. Keller、Christopher S. Callam、Todd L. Lowary

  DOI：10.1016/s0957-4166(03)00078-8

  日期：2003.3

  Two routes for the synthesis of the marine natural product trans-laurediol 6 are described. In the first approach 6 is obtained in ten steps and 21% overall yield from monoacetone D-glucose. The second route provides the target in eleven steps and 13% yield from D-mannose. Both routes are more efficient, both in terms of number of steps and overall yield, than previously reported syntheses. (C) 2003 Elsevier Science Ltd. All rights reserved.
• FUKUZAWA, AKIO;AYE, MYA;MURAI, AKIO, CHEM. LETT.,(1990) N, C. 1579-1580
  作者：FUKUZAWA, AKIO、AYE, MYA、MURAI, AKIO

  DOI：——

  日期：——
• A short synthesis of trans-(+)-laurediol
  作者：Tomás Martı́n、Vı́ctor S Martı́n

  DOI：10.1016/s0040-4039(00)00190-8

  日期：2000.4

  A highly convergent and short synthesis of trans-(+)-laurediol is presented. The synthesis features a highly efficient construction of a cis-3-hydroxy-γ-butyrolactone through a Sharpless AD reaction of a β,γ-unsaturated ester.

  提出了一种高度收敛和短合成的反式-（+）-月桂二醇。该合成具有通过β，γ-不饱和酯的Sharpless AD反应高效地构建顺式3-羟基-γ-丁内酯的特征。