[(4,5-Dihydro-3H-pyrrol-2-ylsulfanyl)]-phenyl-acetic acid methyl ester | 676438-30-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(4,5-Dihydro-3H-pyrrol-2-ylsulfanyl)]-phenyl-acetic acid methyl ester
• 英文别名: methyl 2-(3,4-dihydro-2H-pyrrol-5-ylsulfanyl)-2-phenylacetate
• CAS: 676438-30-5
• 化学式: C₁₃H₁₅NO₂S
• 分子量: 249.334
• InChiKey: VVEFMGPKJPRNQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  64
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(4,5-Dihydro-3H-pyrrol-2-ylsulfanyl)]-phenyl-acetic acid methyl ester 在 platinum(IV) oxide 氢气 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 (+/-)-erythro-methyl 2-phenyl-2-(2-azacyclopentyl)acetate
  参考文献：
  名称：

  The influence of the ring size of thiolactams in the Eschenmoser coupling reaction in presence of DBU. Formation of bicyclic thiazolidinones or thioimines

  摘要：

  The different behaviors of pyrrolidin-2-thione and piperidin-2-thione under a modified Eschenmoser sulfur contraction reaction protocol using DBU as base was observed. The pyrrolidin-2-thione lb follows the expected reaction course, leading to thioimines 5a-d. which can be transformed subsequently into the respective by action of a thiophile, while the piperidin-2-thione leads to the formation of bicyclic thiazolidinones 4b-d in moderate to good yields. The -enaminocarbonyl compound 11 was hydrogenated to afford the respective five-membered analogue of methylphenidate 12. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.12.049
• 作为产物：
  描述：

  四氢吡咯-2-硫酮 、 α-溴苯乙酸甲酯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到[(4,5-Dihydro-3H-pyrrol-2-ylsulfanyl)]-phenyl-acetic acid methyl ester
  参考文献：
  名称：

  The influence of the ring size of thiolactams in the Eschenmoser coupling reaction in presence of DBU. Formation of bicyclic thiazolidinones or thioimines

  摘要：

  The different behaviors of pyrrolidin-2-thione and piperidin-2-thione under a modified Eschenmoser sulfur contraction reaction protocol using DBU as base was observed. The pyrrolidin-2-thione lb follows the expected reaction course, leading to thioimines 5a-d. which can be transformed subsequently into the respective by action of a thiophile, while the piperidin-2-thione leads to the formation of bicyclic thiazolidinones 4b-d in moderate to good yields. The -enaminocarbonyl compound 11 was hydrogenated to afford the respective five-membered analogue of methylphenidate 12. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.12.049

文献信息

• Studies on the Eschenmoser coupling reaction and insights on its mechanism. Application in the synthesis of Norallosedamine and other alkaloids
  作者：Brenno A.D. Neto、Alexandre A.M. Lapis、Alinne B. Bernd、Dennis Russowsky

  DOI：10.1016/j.tet.2009.01.081

  日期：2009.3

  The conditions of the Eschenmoser coupling reaction were studied. The formation of the alpha-thioiminium ion was achieved faster in the presence of an additive (Nal) and dry chloroform as the preferred solvent. The developed conditions were used for the second part of the reaction (the sulfur extrusion itself). The present protocol avoids the formation of byproducts, which were previously described as a major drawback to be overcome. Electrospray ionization tandem mass spectrometry was used to characterize some aspects (intermediates) of the first step of the reaction mechanism. Some reduction conditions were properly tested and the selected conditions were applied to the synthesis of the natural alkaloid Norallosedamine and other derivatives. (C) 2009 Elsevier Ltd. All rights reserved.