(1S,4R)-4-(tert-butoxycarbonylamino)cyclopent-2-enyl 2,2,2-trifluoroethyl malonate | 1187424-54-9

• 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: (1S,4R)-4-(tert-butoxycarbonylamino)cyclopent-2-enyl 2,2,2-trifluoroethyl malonate
• 英文别名: 3-O-[(1S,4R)-4-[(2-methylpropan-2-yl)oxycarbonylamino]cyclopent-2-en-1-yl] 1-O-(2,2,2-trifluoroethyl) propanedioate
• CAS: 1187424-54-9
• 化学式: C₁₅H₂₀F₃NO₆
• 分子量: 367.322
• InChiKey: HSUZXGUKFHNNAU-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  90.9
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (1S,4R)-4-(tert-butoxycarbonylamino)cyclopent-2-enyl 2,2,2-trifluoroethyl malonate 在 盐酸 、 二异丁基氢化铝 、 三乙胺 、 1,2-双(二苯基膦)乙烷 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 、 乙醇 、 水 、 正丁醇 为溶剂， 反应 106.0h， 生成 (+)-2-((1R,4R)-4-(2-amino-6-chloropyrimidin-4-ylamino)cyclopent-2-enyl)ethanol
  参考文献：
  名称：

  Enantioselective syntheses of carbocyclic nucleosides 5′-homocarbovir, epi-4′-homocarbovir, and their cyclopropylamine analogs using facially selective Pd-mediated allylations

  摘要：

  Carbocyclic nucleosides (-)-5'-homocarbovir and (+)-epi-4'-homocarbovir were prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct. A kinetic enzymatic resolution generated an enantiopure aminocyclopentenol and Pd(0)-mediated decarboxylative allylations of allyl 2,2,2-trifluoroethyl malonates were used to install the 4'-hydroxyethyl groups. Late stage derivatization gave access to the cyclopropylamine analogs, (-)-5'-homoabacavir, and (+)-epi-4'-homoabacavir. All carbonucleoside target molecules were evaluated for antiviral activity. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.097
• 作为产物：
  描述：

  (1S,4R)-乙酸-4-叔丁氧羰基氨基-环戊基-2-烯酯 在 甲醇 、 4-二甲氨基吡啶 、 potassium carbonate 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 (1S,4R)-4-(tert-butoxycarbonylamino)cyclopent-2-enyl 2,2,2-trifluoroethyl malonate
  参考文献：
  名称：

  Enantioselective syntheses of carbocyclic nucleosides 5′-homocarbovir, epi-4′-homocarbovir, and their cyclopropylamine analogs using facially selective Pd-mediated allylations

  摘要：

  Carbocyclic nucleosides (-)-5'-homocarbovir and (+)-epi-4'-homocarbovir were prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct. A kinetic enzymatic resolution generated an enantiopure aminocyclopentenol and Pd(0)-mediated decarboxylative allylations of allyl 2,2,2-trifluoroethyl malonates were used to install the 4'-hydroxyethyl groups. Late stage derivatization gave access to the cyclopropylamine analogs, (-)-5'-homoabacavir, and (+)-epi-4'-homoabacavir. All carbonucleoside target molecules were evaluated for antiviral activity. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.097

文献信息

• Palladium-Catalyzed Decarboxylative Rearrangements of Allyl 2,2,2-Trifluoroethyl Malonates: Direct Access to Homoallylic Esters
  作者：Lawrence P. Tardibono、Jerod Patzner、Cara Cesario、Marvin J. Miller

  DOI：10.1021/ol901518g

  日期：2009.9.17

  from allyl 2,2,2-trifluoroethyl malonates by using a Pd(0) catalyst. Facile decarboxylation of allyl 2,2,2-trifluoroethyl malonates is attributed to a decrease in pKa compared to allyl methyl malonates. Subsequent reduction of the homoallylic 2,2,2-trifluoroethyl ester provides a (hydroxyethyl)cyclopentenyl derivative that represents a key intermediate in the synthesis of carbocyclic nucleosides. A select

  通过使用 Pd(0) 催化剂，从丙二酸烯丙酯 2,2,2-三氟乙酯单次转化即可获得高烯丙酯。与烯丙基甲基丙二酸酯相比，烯丙基 2,2,2-三氟乙基丙二酸酯的轻松脱羧归因于 p K a的降低。随后将高烯丙基 2,2,2-三氟乙酯还原得到（羟乙基）环戊烯基衍生物，它是碳环核苷合成中的关键中间体。精选的 2,2,2-三氟乙基丙二酸烯丙酯经过脱羧克莱森重排以提供区域异构的高烯丙基酯。