(R)-1-benzyl-5-thioxoproline tert-butyl ester | 90741-32-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (R)-1-benzyl-5-thioxoproline tert-butyl ester
• 英文别名: tert-butyl (2R)-1-benzyl-5-sulfanylidenepyrrolidine-2-carboxylate
• CAS: 90741-32-5
• 化学式: C₁₆H₂₁NO₂S
• 分子量: 291.414
• InChiKey: YYJIVJFCPCPWEX-CYBMUJFWSA-N

物化性质

• 沸点：
  392.5±52.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-1-benzyl-5-thioxoproline tert-butyl ester 在 劳森试剂 作用下， 生成 (S)-1-Benzyl-5-[4-methoxycarbonyl-2-thioxo-but-(E)-ylidene]-pyrrolidine-2-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Chirospecific syntheses of nitrogen and side-chain-modified anatoxin analogs. Synthesis of (1R)-anatoxinal and (1R)-anatoxinic acid derivatives

  摘要：

  DOI：

  10.1021/jo00296a050
• 作为产物：
  描述：

  (R)-1-Benzyl-5-oxo-pyrrolidine-2-carbonyl chloride 在 吡啶 、 tetraphosphorus decasulfide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 23.0h， 生成 (R)-1-benzyl-5-thioxoproline tert-butyl ester
  参考文献：
  名称：

  Chirospecific syntheses of (+)- and (-)-anatoxin a

  摘要：

  DOI：

  10.1021/ja00328a040

文献信息

• Synthetic and conformational studies on anatoxin-a: a potent acetylcholine agonist
  作者：Ari M. P. Koskinen、Henry Rapoport

  DOI：10.1021/jm00147a032

  日期：1985.9

  Anatoxin-a is a powerful nicotinic acetylcholine receptor agonist. Its recently reported synthesis has been further optimized to provide anatoxin-a of greater than 99% optical purity in 10% overall yield. The geometry of solid anatoxin-a has been determined by X-ray crystallography of its hydrochloride. The solution conformation has been determined by 500-MHz 1H NMR spectroscopy, utilizing 2D NMR methods

  Anatoxin-a是一种强大的烟碱乙酰胆碱受体激动剂。其最近报道的合成方法已得到进一步优化，可提供10％的总收率提供大于99％光学纯度的抗毒素a。固体抗毒素-a的几何形状已通过其盐酸盐的X射线晶体学测定。使用2D NMR方法和同核解偶联，通过500-MHz 1H NMR光谱确定了溶液的构象。为了进一步比较，已使用力场计算来评估可用于抗毒素a的各种构型之间的能量差异。可以看出该分子在溶液和晶体中都采用相同的环构象。
• Conformationally Constrained Analogs of Anatoxin. Chirospecific Synthesis of s-Trans Carbonyl Ring-Fused Analogs
  作者：Andres Hernandez、Henry Rapoport

  DOI：10.1021/jo00084a023

  日期：1994.3

  Anatoxin is the most potent agonist known for the nicotinic acetylcholine receptor (nAChR). Although it possesses a semirigid structure, it can adopt four distinctly different conformations. Further conformationally constrained analogues of anatoxin should help to refine and discriminate among the current models for activation of this receptor. This report describes three s-trans ring-fused analogues which have been synthesized starting from D-glutamic acid and 3-hydroxyacetophenone. All of them have in common a 3-oxo-13-azatricyclo[8.2.1.0(2,7)]trideclane structure. They represent the first fully constrained analogues of anatoxin and are designed to serve as probes of the bioactive conformation of anatoxin at the acetylcholine nicotinic receptor site.
• Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from <scp>d</scp>- and <scp>l</scp>-Glutamic Acid
  作者：Ronghui Lin、Josep Castells、Henry Rapoport

  DOI：10.1021/jo980153t

  日期：1998.6.1

  Natural (-)-cocaine and unnatural (+)-cocaine have been synthesized enantiospecifically from D- and L-glutamic acid, respectively. The axial-equatorial substitutents were introduced by a stereo- and regiospecific dipolar cycloaddition to the corresponding (LR,5S)- and (1S,5R)-N-BOC-nortropenes with (ethoxycarbonyl)formonitrile N-oxide. A sequence of subsequent stereochemically controlled transformations converted the fused isoxazoline to the requisite P-hydroxy ester. Synthesis of the key intermediate N-BOC-nortropenes involved construction of the 8-azabicyclo[3.2.1]octane framework by Dieckmann condensation of cis-5-substituted D-and L-proline esters. For comparison, (1R,SS)-N-BOC-nortropene also was derived by degradation from natural cocaine. The cis-5-substituted D-and L-proline esters were obtained by sulfide contraction and subsequent catalytic hydrogenation to induce stereospecifically the C-5 stereochemistry from D-and L-thiopyroglutamate, which in turn were prepared from D-and L-glutamic acids, respectively.