trans-4-Acetoxy-1-(benzyloxycarbonyl)-D-proline tert-butyl ester | 159487-61-3

• 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: trans-4-Acetoxy-1-(benzyloxycarbonyl)-D-proline tert-butyl ester
• 英文别名: 1-O-benzyl 2-O-tert-butyl (2R,4S)-4-acetyloxypyrrolidine-1,2-dicarboxylate
• CAS: 159487-61-3
• 化学式: C₁₉H₂₅NO₆
• 分子量: 363.411
• InChiKey: TUIWPTWWQWKCNB-JKSUJKDBSA-N

物化性质

• 沸点：
  454.8±45.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  trans-4-Acetoxy-1-(benzyloxycarbonyl)-D-proline tert-butyl ester 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.75h， 以99%的产率得到(2R,4S)-1-(Benzyloxycarbonyl)-4-hydroxyproline tert-butyl ester
  参考文献：
  名称：

  Synthesis of Conformationally Constrained DTPA Analogs. Incorporation of the Ethylenediamine Units as Aminopyrrolidines

  摘要：

  The synthesis of conformationally constrained diethylenetriaminepentaacetic acid (DTPA) analogues is an effort to probe the relationship between ligand structure and metal complex stability. In the pursuit of this objective, diastereomerically and enantiomerically pure mono- and bis-pyrrolidine analogues of DTPA have been prepared from trans-4-hydroxy-L-proline. The mono-pyrrolidine chelator 1 was constructed from a single hydroxyproline unit and an ethylenediamine moiety while two hydroxyproline-derived fragments 4e or 14b and 9b were coupled by N-alkylation of a triflate to afford the core bis-pyrrolidine structures: optically active 10 and meso-15. Deprotection of the triamine pentaesters 12 and 17 afforded the triamine pentaacetic acids 2 and 3 as their hydrochloride salts. The stereochemical homogeneity of precursor esters 12 and 17 was determined by HPLC using authentic epimeric standards to establish that essentially no racemization of the original amino acid a-center had occurred. Some loss of stereochemical homogeniety was encountered in the synthesis of 10 and 15 by N-alkylation of aminoproline 9b with a hydroxyproline-derived triflate, which had proceeded with some retention of configuration. The diastereomeric impurities were removed by crystallization of the respective benzyl carbamates. Bis-pyrrolidine pentaacids 2 and 3 formed isolable chelates with gadolinium and lutetium. A comparision of the lutetium chelates of 2 and 3 by NMR revealed significant differences which were reflective of a rigid structure with 2, while metal complexation with 3 was structurally less defined.

  DOI：

  10.1021/jo00092a022
• 作为产物：
  描述：

  顺式-4-羟基-D-脯氨酸盐酸盐 在 碳酸氢钠 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 42.5h， 生成 trans-4-Acetoxy-1-(benzyloxycarbonyl)-D-proline tert-butyl ester
  参考文献：
  名称：

  Synthesis of Conformationally Constrained DTPA Analogs. Incorporation of the Ethylenediamine Units as Aminopyrrolidines

  摘要：

  The synthesis of conformationally constrained diethylenetriaminepentaacetic acid (DTPA) analogues is an effort to probe the relationship between ligand structure and metal complex stability. In the pursuit of this objective, diastereomerically and enantiomerically pure mono- and bis-pyrrolidine analogues of DTPA have been prepared from trans-4-hydroxy-L-proline. The mono-pyrrolidine chelator 1 was constructed from a single hydroxyproline unit and an ethylenediamine moiety while two hydroxyproline-derived fragments 4e or 14b and 9b were coupled by N-alkylation of a triflate to afford the core bis-pyrrolidine structures: optically active 10 and meso-15. Deprotection of the triamine pentaesters 12 and 17 afforded the triamine pentaacetic acids 2 and 3 as their hydrochloride salts. The stereochemical homogeneity of precursor esters 12 and 17 was determined by HPLC using authentic epimeric standards to establish that essentially no racemization of the original amino acid a-center had occurred. Some loss of stereochemical homogeniety was encountered in the synthesis of 10 and 15 by N-alkylation of aminoproline 9b with a hydroxyproline-derived triflate, which had proceeded with some retention of configuration. The diastereomeric impurities were removed by crystallization of the respective benzyl carbamates. Bis-pyrrolidine pentaacids 2 and 3 formed isolable chelates with gadolinium and lutetium. A comparision of the lutetium chelates of 2 and 3 by NMR revealed significant differences which were reflective of a rigid structure with 2, while metal complexation with 3 was structurally less defined.

  DOI：

  10.1021/jo00092a022