E-(-)-benzylidenepyruvate de menthyle | 110143-65-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: E-(-)-benzylidenepyruvate de menthyle
• 英文别名: l-menthyl benzylidenepyruvate；(E)-l-menthyl 2-oxo-4-phenylbut-3-enoate；2-oxo-4-phenylbut-3-enoic acid 2-isopropyl-5-methylcyclohexyl ester；[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] (E)-2-oxo-4-phenylbut-3-enoate
• CAS: 110143-65-2
• 化学式: C₂₀H₂₆O₃
• 分子量: 314.425
• InChiKey: SODPQZYHRWLODB-QCGCAAMNSA-N

物化性质

• 沸点：
  427.3±28.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  E-(-)-benzylidenepyruvate de menthyle 在 palladium on activated charcoal 吡啶 、 盐酸 、 氢氧化钾 、 硫酸 、 氢气 、 sodium hydride 、 三乙胺 作用下， 以 1,4-二氧六环 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 50.0 ℃ 、303.98 kPa 条件下， 反应 74.5h， 生成 盐酸替莫普利
  参考文献：
  名称：

  Angiotensin-converting enzyme inhibitors. Perhydro-1,4-thiazepin-5-one derivatives

  摘要：

  alpha-[6-[[(S)-1-(Ethoxycarbonyl)-3-phenylpropyl]amino]-5-oxoperhydro -1,4-thiazepin-4-yl]acetic acids (monoester monoacids) and their dicarboxylic acids having the hydrophobic substituents at the 2- or 3-position of the thiazepinone ring were prepared and assayed for angiotensin-converting enzyme (ACE) inhibitory activity. The dicarboxylic acids having the pseudoequatorial amino groups at the 6-position and the pseudoequatorial hydrophobic substituents at the 2- or 3-position of the chair conformation of the thiazepinone ring had potent in vitro inhibitory activity. The monoester monoacids having the hydrophobic substituents at the 2-position suppressed pressor response to angiotensin I for a longer duration than those having the substituents at the 3-position when administered orally. The structure-activity relationship was studied by conformational energy calculations of the thiazepinone ring.

  DOI：

  10.1021/jm00394a009
• 作为产物：
  描述：

  potassium (E)-2-oxo-4-phenylbut-3-enoate 在 盐酸 、 1,1-二氯甲醚 、 三乙胺 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.0h， 生成 E-(-)-benzylidenepyruvate de menthyle
  参考文献：
  名称：

  水飞蓟宾新酸性代谢物的结构和绝对构型

  摘要：

  从地碱（Stachys ehrenberiigii）的地上部分分离出两种新的代谢产物。结合13 C和1 H同质和异核2D NMR实验和质量分析，阐明了它们的结构和立体化学。对3-（2'-乙酰氧基-4-苯基丁-3'-烯酰氨基）丙酸的对映选择性合成的发展允许确认结构并在天然产物的C-2'处赋予（R）绝对构型。

  DOI：

  10.1016/j.tetlet.2011.08.143

文献信息

• Tertiary Amine Mediated Tandem Cross-Rauhut-Currier/Acetalization Reactions: Access to Functionalized Spiro-3,4-Dihydropyrans
  作者：Weijun Yao、Yihua Wu、Gang Wang、Yiping Zhang、Cheng Ma

  DOI：10.1002/anie.200905091

  日期：2009.12.14

  γ‐Proton transfer furnished the highly selective title reaction in which cyclic β‐haloenals 1 react with β,γ‐unsaturated α‐ketoesters 2 to generate functionalized spiro‐3,4‐dihydro‐2H‐pyrans 3 having an α‐quaternary carbon center and an adjacent vinyl halide group in skeleton. DBU=1,8‐diazabicyclo[5.4.0]undec‐7‐ene, Tos=4‐toluenesulfonyl.

  γ-质子传递布置，其中环状β-haloenals高度选择性标题反应1与β，γ不饱和α酮酯反应2来生成官能螺-3,4-二氢-2 ħ -pyrans 3具有α-季碳中心和骨架中相邻的乙烯基卤化物基团。DBU ＝ 1，8-二氮杂双环[5.4.0]十一月-7-烯，Tos ＝ 4-甲苯磺酰基。
• Asymmetric endoselective [4+2] heterocycloadditions of styrene dienophiles with chiral benzylidenepyruvic esters. Total synthesis of (−)-O-dimethylsugiresinol
  作者：Gilles Dujardin、Mickaël Maudet、Eric Brown

  DOI：10.1016/s0040-4039(97)00144-5

  日期：1997.3

  Eu(fod)3 catalyzed [4+2] heterocycloadditions of para-methoxystyrene 7 with esters 8a-f of benzylidenepyruvic acids (deriving from various chiral alcohols) furnished endo adducts 9a-f with variable diastereoselective ratios (from to ). Interestingly, the benzylidenepyruvic esters 8g and 8h, deriving from a new chiral vector, the α-O-silyl ether 6 of (D)-(−)-erythronolactone 5, gave the corresponding

  铕（FOD）3催化的[4 + 2]的heterocycloadditions第-methoxystyrene 7与酯8A-F的benzylidenepyruvic酸（来自各种手性醇导出）家具内加合物9A-F具有可变非对映选择性比（从至）。有趣的是，benzylidenepyruvic酯8克和8H，从一个新的手性载体，所述导出α - ø -甲硅烷基醚6（ - ） - - （d）的erythronolactone 5，得到相应的内切加合物9克和9H非对映选择性高（）的化合物。加合物9h被用作“天然”（-）-二甲基sugiresinol（1b）的五步合成中的前体。
• Synthèse asymétrique et configuration absolue de dihydropyranes substitués, par hétérocycloaddition intermoléculaire d'éthers vinyliques chiraux
  作者：Gilles Dujardin、Sandrine Rossignol、Samira Molato、Eric Brown

  DOI：10.1016/s0040-4020(01)85370-9

  日期：1994.1

  The alkyl vinyl ethers 2b-8b (deriving from the alcohols 2a-8a) smoothly reacted with methyl E-benzylidenepyruvate 10 in the presence of catalytic amounts of Eu(fod)(3) or Yb(fod)(3) in refluxing hexane, thus leading to the dihydropyran endo adducts 13-19 in high yields (80-95%). The endo-cycloadducts 13-17 were obtained with diastereofacial selectivities (ds) ranging from 76/24 to 87.5/12.5. Asymmetric induction was found to culminate with the vinyl ether (-)-7b deriving from n-butyl (R)-(-)-mandelate : the best ds (92.5/7.5) was obtained for the corresponding adduct 18 after 6 days at room temperature. The absolute configurations of the major isomers of the dihydropyrans 16-18, 20 and 21 were established by oxydative degradation to optically active alpha-phenylsuccinic acid derivatives.
• YANAGISAWA, HIROAKI;ISHIHARA, SADAO;ANDO, AKIKO;KANAZAKI, TAKURO;MIYAMOTO+, J. MED. CHEM., 30,(1987) N 11, 1984-1991
  作者：YANAGISAWA, HIROAKI、ISHIHARA, SADAO、ANDO, AKIKO、KANAZAKI, TAKURO、MIYAMOTO+

  DOI：——

  日期：——
• Angiotensin-converting enzyme inhibitors. Perhydro-1,4-thiazepin-5-one derivatives
  作者：Hiroaki Yanagisawa、Sadao Ishihara、Akiko Ando、Takuro Kanazaki、Shuichi Miyamoto、Hiroyuki Koike、Yasuteru Iijima、Kiyoshi Oizumi、Yoichi Matsushita、Tadashi Hata

  DOI：10.1021/jm00394a009

  日期：1987.11

  alpha-[6-[[(S)-1-(Ethoxycarbonyl)-3-phenylpropyl]amino]-5-oxoperhydro -1,4-thiazepin-4-yl]acetic acids (monoester monoacids) and their dicarboxylic acids having the hydrophobic substituents at the 2- or 3-position of the thiazepinone ring were prepared and assayed for angiotensin-converting enzyme (ACE) inhibitory activity. The dicarboxylic acids having the pseudoequatorial amino groups at the 6-position and the pseudoequatorial hydrophobic substituents at the 2- or 3-position of the chair conformation of the thiazepinone ring had potent in vitro inhibitory activity. The monoester monoacids having the hydrophobic substituents at the 2-position suppressed pressor response to angiotensin I for a longer duration than those having the substituents at the 3-position when administered orally. The structure-activity relationship was studied by conformational energy calculations of the thiazepinone ring.