methyl (3R,4R,4'S)-(-)-3-N-benzyloxycarbonylamino-4-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-pyrazoline-3-carboxylate | 160002-53-9

• 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: methyl (3R,4R,4'S)-(-)-3-N-benzyloxycarbonylamino-4-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-pyrazoline-3-carboxylate
• 英文别名: methyl (4R,5R)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-5-(phenylmethoxycarbonylamino)-3,4-dihydropyrazole-5-carboxylate
• CAS: 160002-53-9
• 化学式: C₁₈H₂₃N₃O₆
• 分子量: 377.397
• InChiKey: SZTIRTQKESYPEF-PMUMKWKESA-N

物化性质

• 沸点：
  500.5±50.0 °C(predicted)
• 密度：
  1.35±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl (3R,4R,4'S)-(-)-3-N-benzyloxycarbonylamino-4-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-pyrazoline-3-carboxylate 在 palladium dihydroxide 1,3-二甲基-2-苯基-2-磷杂咪唑烷 、 盐酸 、 甲醇 、 sodium hydroxide 、 二苯甲酮 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， -78.0~40.0 ℃ 、101.33 kPa 条件下， 反应 194.8h， 生成 (1S,2R)-1-氨基-2-乙基环丙烷羧酸
  参考文献：
  名称：

  Enantioselective total syntheses of cyclopropane amino acids: Natural products and protein methanologs

  摘要：

  The syntheses of (-)-allo-coronamic acid, (-)-allo-norcoronamic acid, (-)-(Z)-2, 3-methanohomoserine, (-)-(Z)-2, 3-methanomethionine, and (2S, 3R)-Cbz-cyclo-Asp-OMe have been achieved in 45-68% overall yields from suitable intermediates derived from homochiral aminopentenoates which were obtained, in bun, from D-glyceraldehyde. The key synthetic step involves the quantitative and highly diastereoselective cyclopropanation of such precursors. The factors dealing with the control of stereoselectivity are highlighted and the main features in sidechain functionalization to the respective target molecules are discussed.

  DOI：

  10.1016/0957-4166(96)00038-9
• 作为产物：
  描述：

  (±)-Z-α-膦酰甘氨酸三甲酯 在 potassium tert-butylate 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 methyl (3R,4R,4'S)-(-)-3-N-benzyloxycarbonylamino-4-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-pyrazoline-3-carboxylate
  参考文献：
  名称：

  Enantioselective total syntheses of cyclopropane amino acids: Natural products and protein methanologs

  摘要：

  The syntheses of (-)-allo-coronamic acid, (-)-allo-norcoronamic acid, (-)-(Z)-2, 3-methanohomoserine, (-)-(Z)-2, 3-methanomethionine, and (2S, 3R)-Cbz-cyclo-Asp-OMe have been achieved in 45-68% overall yields from suitable intermediates derived from homochiral aminopentenoates which were obtained, in bun, from D-glyceraldehyde. The key synthetic step involves the quantitative and highly diastereoselective cyclopropanation of such precursors. The factors dealing with the control of stereoselectivity are highlighted and the main features in sidechain functionalization to the respective target molecules are discussed.

  DOI：

  10.1016/0957-4166(96)00038-9

文献信息

• 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Electron-Deficient Olefins:  The Origin of the π-Facial Diastereoselection
  作者：Elena Muray、Angel Alvarez-Larena、Joan F. Piniella、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo991227j

  日期：2000.1.1

  The stereochemical outcome of diazomethane cycloadditions to several chiral electron-deficient olefins has been investigated in order to establish the origin of the pi-facial diastereoselection. Nitro olefins, vinyl sulfones, enoates, and 2-amino enoates have been used for such a purpose. These substrates have been prepared from D-glyceraldehyde acetonide through Wittig-type condensations and present

  研究了重氮甲烷环加成到几种手性电子缺陷烯烃上的立体化学结果，以便确定pi非对映选择性的起源。硝基烯烃，乙烯基砜，烯酸酯和2-氨基烯酸酯已用于此目的。这些底物是由D-甘油醛丙酮化物通过Wittig型缩合反应制得的，并具有一个由庞大的二氧戊环提供的烷氧基取代基，该取代基与立体异构的烯丙基碳相连。在所有情况下，均已获得作为主要异构体的加合物，而与双键的Z / E立体化学以及取代基的数量和性质无关，不对称烯丙基碳的手性是造成非对映异构的唯一原因。
• Highly efficient and stereocontrolled synthetic route to enantiopure ACC derivatives
  作者：José M. Jiménez、Ramon Casas、Rosa M. Ortuño

  DOI：10.1016/s0040-4039(00)78226-8

  日期：1994.8

  Highly diastereoselective cyclopropanation of a chiral α,β-dehydroamino acid derivative, obtained from D-mannitol, leads to a single isomer which has been transformed into the title compound in 65% overall yield. This product can be a useful intermediate in the synthesis of enantiopure ACC derivatives.

  由D-甘露糖醇获得的手性α，β-脱氢氨基酸衍生物的高度非对映选择性环丙烷化产生单一异构体，该异构体以65％的总收率转化为标题化合物。该产物可能是合成对映纯ACC衍生物的有用中间体。
• Synthesis and photochemical decomposition of pyrazolines from homochiral amino pentenoates. A laser flash-photolysis study
  作者：JoséM. Jiménez、JoséL. Bourdelande、Rosa M. Ortuño

  DOI：10.1016/s0040-4020(97)00098-7

  日期：1997.3

  order to find the optimal conditions and to establish the influence of sensitizers. The transient behaviour of the pyrazoline triplet state has been analyzed by laser flash photolysis either after direct excitation or after energy transfer from benzophenone.

  光学纯的吡唑啉是通过将重氮甲烷环加成到手性氨基戊烯酸酯上而合成的，取决于前体的立体化学，面部非对映选择性是相反的。已显示这些吡唑啉光分解为相应的环丙烷是立体定向的，并且已经进行了研究，以找到最佳条件并建立敏化剂的影响。直接激发后或从二苯甲酮转移能量后，通过激光闪光光解法分析了吡唑啉三重态的瞬态行为。