(2E,4S,11R)-11-Hydroxy-4-(tert-butyldimethylsiloxy)-2-dodecenecarboxylic acid | 124887-10-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (2E,4S,11R)-11-Hydroxy-4-(tert-butyldimethylsiloxy)-2-dodecenecarboxylic acid
• 英文别名: (E,4S,11R)-4-[tert-butyl(dimethyl)silyl]oxy-11-hydroxydodec-2-enoic acid
• CAS: 124887-10-1
• 化学式: C₁₈H₃₆O₄Si
• 分子量: 344.567
• InChiKey: QRZJFXCOGXNCAS-WVJKRLJDSA-N

物化性质

• 沸点：
  443.1±40.0 °C(Predicted)
• 密度：
  0.972±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  23
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2E,4S,11R)-11-Hydroxy-4-(tert-butyldimethylsiloxy)-2-dodecenecarboxylic acid 在 四丁基氟化铵 、 2,6-二氯苯甲酰氯 作用下， 以 四氢呋喃 、 二乙胺 、 甲苯 为溶剂， 生成 (5S,12R)-5-hydroxyy-12-methyl-1-oxa-3-cyclododecen-2-one
  参考文献：
  名称：

  大环内酯Patulolide C的对映选择性全合成

  摘要：

  描述了十二元环内酯帕特洛立德C的全合成。这种合成的基本要素是：R-甲基环氧乙烷与乙炔锂的亲核开环，无尖锐的环氧化，将环氧重氮甲基酮进行光化学重排为γ-羟基-α，β-不饱和酯和大分子使用2，6-二氯苯甲酰氯进行内酯化。

  DOI：

  10.1016/s0040-4039(01)93736-0
• 作为产物：
  描述：

  2-(hex-5-yn-1-yloxy)tetrahydro-2H-pyran 在 4-二甲氨基吡啶 、 palladium on activated charcoal 吡啶 、 咪唑 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 sodium hydroxide 、 sodium periodate 、 正丁基锂 、 草酰氯 、 4 A molecular sieve 、 四丁基氟化铵 、 氢气 、 四丁基碘化铵 、 sodium hydride 、 二异丁基氢化铝 、 对甲苯磺酸 、 二甲基亚砜 、 (+)-Weinsaeure-diethylester 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 六甲基磷酰三胺 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 28.58h， 生成 (2E,4S,11R)-11-Hydroxy-4-(tert-butyldimethylsiloxy)-2-dodecenecarboxylic acid
  参考文献：
  名称：

  Total synthesis of patulolide C and its homo-, nor, and iso analogs

  摘要：

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.

  DOI：

  10.1021/jo00077a047

文献信息

• An enantioselective total synthesis of the macrolide Patulolide C
  作者：L. Thijs、D.M. Egenberger、B. Zwanenburg

  DOI：10.1016/s0040-4039(01)93736-0

  日期：1989.1

  described. The essentials of this synthesis are: nucleophilic ring opening of R-methyloxirane with a lithium acetylide, a Sharpless epoxidation, strategic use of the photochemical rearrangement of an epoxy diazomethyl ketone to a γ-hydroxy-α,β-unsaturated ester and a macro-lactonization using 2,6-dichlorobenzoyl chloride.

  描述了十二元环内酯帕特洛立德C的全合成。这种合成的基本要素是：R-甲基环氧乙烷与乙炔锂的亲核开环，无尖锐的环氧化，将环氧重氮甲基酮进行光化学重排为γ-羟基-α，β-不饱和酯和大分子使用2，6-二氯苯甲酰氯进行内酯化。
• THIJS, L.;EGENBERGER, D. M.;ZWANENBURG, B., TETRAHEDRON LETT., 30,(1989) N6, C. 2153-2156
  作者：THIJS, L.、EGENBERGER, D. M.、ZWANENBURG, B.

  DOI：——

  日期：——
• Total synthesis of patulolide C and its homo-, nor, and iso analogs
  作者：Frank M. C. Leemhuis、Lambertus Thijs、Binne Zwanenburg

  DOI：10.1021/jo00077a047

  日期：1993.12

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.