caldarchaeol | 99529-31-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: caldarchaeol
• 英文别名: [(2R,7R,11R,15S,19S,22S,26S,30R,34R,38R,43R,47R,51S,55S,58S,62S,66R,70R)-38-(hydroxymethyl)-7,11,15,19,22,26,30,34,43,47,51,55,58,62,66,70-hexadecamethyl-1,4,37,40-tetraoxacyclodoheptacont-2-yl]methanol
• CAS: 99529-31-4
• 化学式: C₈₆H₁₇₂O₆
• 分子量: 1302.31
• InChiKey: VMHUDYKDOMRJOK-QUYWEVSVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  34
• 重原子数：
  92
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  caldarchaeol 、 (2S,7R,11R,15S,19S,22S,26S,30R,34R,39S,43R,47R,51S,55S,58S,62S,66R,70R)-2,39-bis(hydroxymethyl)-7,11,15,19,22,26,30,34,43,47,51,55,58,62,66,70-hexadecamethyl-1,4,37,40-tetraoxacyclodoheptacontane 在 吡啶 、 对甲苯磺酰氯 、 sodium iodide 、 锌 作用下， 生成 3,7,11,15,18,22,26,30-八甲基三十二烷-1,32-二醇 、 (3R,7R,11S,15S,18S,22S,26R,30R)-32-Allyloxy-3,7,11,15,18,22,26,30-octamethyl-dotriacontan-1-ol 、 (3R,7R,11S,15S,18S,22S,26R,30R)-1,32-Bis-allyloxy-3,7,11,15,18,22,26,30-octamethyl-dotriacontane
  参考文献：
  名称：

  Detection of regioisomeric macrocyclic tetraethers in the lipids of Methanobacterium thermoautotrophicum and other archaeal organisms

  摘要：

  Chemical degradation shows that an apparently homogeneous preparation from the lipids of Methanobacterium thermoautotrophicum is in fact a mixture of the regioisomeric compounds 2 and 8 differing in the relative orientation of their glycerol units; a similar situation holds for the related diglycerol tetraethers of Thermoplasma acidophilum and Sulfolobus solfataricus.

  DOI：

  10.1039/c39950000405
• 作为产物：
  描述：

  (R)-2,3-bis(((2E,6E,10E)-3,7,11,15-tetramethylhexadeca-2,6,10,15-tetraen-1-yl-14,14-d2)oxy)propan-1-ol 在 4-二甲氨基吡啶 、 二氧化碳 、 Methanothermobacter thermautotrophicus JCM 10044^T 、 氢气 作用下， 以 吡啶 为溶剂， 反应 120.0h， 生成 caldarchaeol
  参考文献：
  名称：

  Importance of the isopropylidene terminal of geranylgeranyl group for the formation of tetraether lipid in methanogenic archaea

  摘要：

  Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the C-C bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this C-C bond formation. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)00627-0

文献信息

• A Unified Approach for the Total Synthesis of <i>cyclo</i> ‐Archaeol, <i>iso</i> ‐Caldarchaeol, Caldarchaeol, and Mycoketide
  作者：Ruben L. H. Andringa、Niels A. W. Kok、Arnold J. M. Driessen、Adriaan J. Minnaard

  DOI：10.1002/anie.202104759

  日期：2021.8.2

  the strategy par excellence to prepare saturated isoprenoids and mycoketides. This highly stereoselective synthesis approach is combined with an established 13C-NMR method to determine the enantioselectivity of each methyl-branched stereocenter. It is shown that this analysis is fit for purpose and the combination allows the synthesis of the title compounds with a significant increase in efficiency

  铱催化的不对称烯烃氢化被认为是制备饱和类异戊二烯和真菌酮化合物的最佳策略。这种高度立体选择性的合成方法与已建立的13 C-NMR 方法相结合，以确定每个甲基支化立体中心的对映选择性。结果表明，该分析符合目的，并且该组合可以显着提高标题化合物的合成效率。
• Total Synthesis of Archaeal 72-Membered Macrocyclic Tetraether Lipids
  作者：Tadashi Eguchi、Kazuya Ibaragi、Katsumi Kakinuma

  DOI：10.1021/jo972328p

  日期：1998.4.1

  Total synthesis of archaeal 72-membered macrocyclic tetraether lipids 3a and 3b is reported. The synthesis was principally composed of preparation of the functionalized half-sized diether compounds 11 and 15 first followed by appropriate dimerization through Julia coupling and final macrocyclization of the crucial dialdehydes 23 and 31 by McMurry coupling. This strategy appeared to be advantageous for the stereoselective synthesis of both natural 72-membered tetraether lipids 3a and 3b using common synthetic intermediates. In addition, this approach was so designed that its synthetic flexibility would allow construction of unnatural structural variants for physicochemical studies. Also described are the results of differential scanning calorimetric analysis of the synthesized lipids 3a and 3b. Both 3a and 3b showed almost the same phase behavior with the broad endothermic phase transition at -53 degrees C. The enthalpy of the phase transition, Delta H, was estimated to be 1.8 and 1.9 kcal/mol for 3a and 3b, respectively. The physicochemical as well as polymorphismic properties of 3a and 3b turned out to be indistinguishable despite of their regioisomeric structures. The physical structure of the phases in terms of the chemical structure is also discussed.
• Importance of the isopropylidene terminal of geranylgeranyl group for the formation of tetraether lipid in methanogenic archaea
  作者：Tadashi Eguchi、Yuji Nishimura、Katsumi Kakinuma

  DOI：10.1016/s0040-4039(03)00627-0

  日期：2003.4

  Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the C-C bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this C-C bond formation. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Detection of regioisomeric macrocyclic tetraethers in the lipids of Methanobacterium thermoautotrophicum and other archaeal organisms
  作者：Otto Gräther、Duilio Arigoni

  DOI：10.1039/c39950000405

  日期：——

  Chemical degradation shows that an apparently homogeneous preparation from the lipids of Methanobacterium thermoautotrophicum is in fact a mixture of the regioisomeric compounds 2 and 8 differing in the relative orientation of their glycerol units; a similar situation holds for the related diglycerol tetraethers of Thermoplasma acidophilum and Sulfolobus solfataricus.