(2R,4S,6R,8S)-2,4,6,8-tetramethylundecan-1-ol | 868061-58-9

• 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: (2R,4S,6R,8S)-2,4,6,8-tetramethylundecan-1-ol
• CAS: 868061-58-9
• 化学式: C₁₅H₃₂O
• 分子量: 228.418
• InChiKey: LPEAEEKHQAZLTI-LJISPDSOSA-N

物化性质

• 沸点：
  273.7±8.0 °C(Predicted)
• 密度：
  0.830±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2R,4S,6R,8S)-2,4,6,8-tetramethylundecan-1-ol 在 palladium on activated charcoal 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 4 Angstroem MS 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 4.58h， 生成 (5S,7R,13S,15R,17R,19S)-5,7,13,15,17,19-hexamethyldocosan-10-one
  参考文献：
  名称：

  Synthesis of (S,R,R,S,R,S)-4,6,8,10,16,18- Hexamethyldocosane from Antitrogus parvulus via Diastereoselective Hydrogenations

  摘要：

  The hydrocarbon 1 was prepared via a series of catalyst-controlled diastereoselective hydrogenations beginning with fragments derived from the Roche ester.

  DOI：

  10.1021/ol070298z
• 作为产物：
  描述：

  (S)-(-)-β-香茅醇 在 咪唑 、 盐酸 、 4-二甲氨基吡啶 、 copper(l) iodide 、 萘 、 bismuth(III) iodide 、 bicyclo[2.2.1]hepta-2,5-diene,4-diphenylphosphanylbutyl(diphenyl)phosphane,rhodium,tetrafluoroborate 、 palladium 10% on activated carbon 、 potassium tert-butylate 、 甲基锂 、 氢气 、 lithium 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 臭氧 、 三苯基膦 、 lithium iodide 、 锌 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 为溶剂， -78.0~20.0 ℃ 、6.55 MPa 条件下， 反应 132.67h， 生成 (2R,4S,6R,8S)-2,4,6,8-tetramethylundecan-1-ol
  参考文献：
  名称：

  Systematic Comparison of Sets of ¹³C NMR Spectra That Are Potentially Identical. Confirmation of the Configuration of a Cuticular Hydrocarbon from the Cane Beetle Antitrogus parvulus

  摘要：

  A systematic process is introduced to compare (13)C NMR spectra of two (or more) candidate samples of known structure to a natural product sample of unknown structure. The process is designed for the case where the spectra involved can reasonably be expected to be very similar, perhaps even identical. It is first validated by using published (13)C NMR data sets for the natural product 4,6,8,10,16,18-hexamethyldocosane. Then the stereoselective total syntheses of two candidate isomers of the related 4,6,8,10,16-pentamethyldocosane natural product are described, and the process is applied to confidently assign the configuration of the natural product as (4S,6R,8R,10S,16S). This is accomplished even though the chemical shift differences between this isomer and its (16R)-epimer are only ±5-10 ppb (±0.005-0.01 ppm).

  DOI：

  10.1021/jo5012027

文献信息

• Total synthesis of a cuticular hydrocarbon from the cane beetle Antitrogus parvulus: confirmation of the relative stereochemistry
  作者：Norazah B. Basar、Hao Liu、Devendra Negi、Hasnah M. Sirat、Gareth A. Morris、Eric J. Thomas

  DOI：10.1039/c2ob06906g

  日期：——

  The stereoselective reaction of an allyl bromide with an aldehyde mediated by a low valency bismuth species was the key reaction in stereoselective syntheses of (4S,6R,8R,10S,16S)- and (4S,6R,8R,10S,16R)-4,6,8,10,16-pentamethyldocosanes. 13C NMR data for these compounds confirmed that the cuticular hydrocarbon isolated from the cane beetle Antitrogus parvulus was the (4S,6R,8R,10S,16S)-stereoisomer.

  在低价铋物种介导下，烯丙基溴与醛的立体选择性反应是合成(4S,6R,8R,10S,16S)-和(4S,6R,8R,10S,16R)-4,6,8,10,16-五甲基二十二烷的关键反应。这些化合物的13C核磁共振数据证实，从甘蔗甲虫Antitrogus parvulus分离得到的蜡质烃为(4S,6R,8R,10S,16S)-立体异构体。
• Single-Step Construction of the <i>anti</i> -Deoxypropionate Motif from Propylene: Formal Total Synthesis of the Cuticular Hydrocarbons Isolated from <i>Antitrogus parvulus</i>
  作者：Toshiki Murayama、Kyoko Nozaki

  DOI：10.1002/anie.201804711

  日期：2018.8.27

  Reported herein is the single‐step construction of an anti‐configured deoxypropionate motif by syndiospecific propylene oligomerization catalyzed by a Cs‐symmetric zirconocene complex. After oligomerization, oxidation of the oligomers by oxygen afforded oligopropylene alcohols in a single step. This strategy was applied to the single‐step preparation of rel‐(2R,4S,6R,8S)‐2,4,6,8‐tetramethylundecan‐1‐ol

  本文报道的是通过C s对称的锆茂复合物催化的间同特异性丙烯低聚反应，一步法构建反构型的脱氧丙酸酯基序。低聚后，通过氧气氧化低聚物，在一步中得到低聚丙醇。该策略适用于rel-（2 R，4 S，6 R，8 S）-2,4,6,8-四甲基十一碳烯-1-醇的单步制备过程，该混合物是外消旋体合成片段的外消旋混合物。从甘蔗甲虫Antitrogus parvulus分离得到的表皮碳氢化合物。
• Enantioselective Total Synthesis and Determination of the Absolute Configuration of the 4,6,8,10,16,18-Hexamethyldocosane fromAntitrogus parvulus
  作者：Christian Herber、Bernhard Breit

  DOI：10.1002/ejoc.200700282

  日期：2007.7

  isolated from the cuticula of Antitrogus parvulus was determined based on the total synthesis of both diastereomers 1a and 1b in enantiomerically pure form. The synthesis demonstrates the utility of the o-DPPB-directed and copper-mediated allylic syn-substitution reaction with Grignard reagents for iterative deoxypropionate construction (o-DPPB = ortho-diphenylphosphanylbenzoyl). Additionally, the synthetic

  基于对映体纯形式的非对映异构体 1a 和 1b 的全合成，确定了从小小蚂蚁的角质层中分离出的六甲基二十二烷 (1) 的绝对和相对构型。该合成证明了 o-DPPB 导向和铜介导的烯丙基合成取代反应与格氏试剂的效用，用于迭代脱氧丙酸酯构建（o-DPPB = 邻二苯基膦酰基苯甲酰基）。此外，还显示了铜催化 sp3-sp3 交叉偶联反应的合成能力，通过双重用于构建块构建和作为收敛全合成过程中的最终片段偶联步骤。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Efficient and Selective Synthesis of (<i>S</i>,<i>R</i>,<i>R</i>,<i>S</i>,<i>R</i>,<i>S</i>)-4,6,8,10,16,18-Hexamethyl- docosane via Zr-Catalyzed Asymmetric Carboalumination of Alkenes (ZACA Reaction)
  作者：Gangguo Zhu、Bo Liang、Ei-ichi Negishi

  DOI：10.1021/ol703056u

  日期：2008.3.1

  (S,R,R,S,R,S)-4,6,8,10,16,18-Hexamethyldocosane (1) was synthesized in 11% yield in 11 steps in the longest linear sequence from > or =98% pure (S)-beta-citronellal and 6 additional steps for the preparation of 11 in 23% yield from propene. Five of the six asymmetric carbon centers were generated catalytically and stereoselectively by the ZACA reaction (5 times), one lipase-catalyzed acetylation, and

  （S，R，R，S，R，S）-4,6,8,10,16,18-六甲基甲基二十二烷（1）以11％的产率按最长线性顺序从11％合成，大于或等于98％纯的（S）-β-香茅醛和6个额外的步骤，以11％的产率从丙烯制备11个。六个不对称碳中心中的五个是通过ZACA反应（5次），一种脂肪酶催化的乙酰化反应和两次色谱操作催化和立体选择性生成的。
• Systematic Comparison of Sets of ¹³C NMR Spectra That Are Potentially Identical. Confirmation of the Configuration of a Cuticular Hydrocarbon from the Cane Beetle <i>Antitrogus parvulus</i>
  作者：Norazah Basar、Krishnan Damodaran、Hao Liu、Gareth A. Morris、Hasnah M. Sirat、Eric J. Thomas、Dennis P. Curran

  DOI：10.1021/jo5012027

  日期：2014.8.15

  A systematic process is introduced to compare (13)C NMR spectra of two (or more) candidate samples of known structure to a natural product sample of unknown structure. The process is designed for the case where the spectra involved can reasonably be expected to be very similar, perhaps even identical. It is first validated by using published (13)C NMR data sets for the natural product 4,6,8,10,16,18-hexamethyldocosane. Then the stereoselective total syntheses of two candidate isomers of the related 4,6,8,10,16-pentamethyldocosane natural product are described, and the process is applied to confidently assign the configuration of the natural product as (4S,6R,8R,10S,16S). This is accomplished even though the chemical shift differences between this isomer and its (16R)-epimer are only ±5-10 ppb (±0.005-0.01 ppm).