(2R,3S)-3-tert-butoxy-1-hydroxypyrrolidine-2-carbonitrile | 405164-80-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2R,3S)-3-tert-butoxy-1-hydroxypyrrolidine-2-carbonitrile
• 英文别名: (2R,3S)-1-hydroxy-3-[(2-methylpropan-2-yl)oxy]pyrrolidine-2-carbonitrile
• CAS: 405164-80-9
• 化学式: C₉H₁₆N₂O₂
• 分子量: 184.238
• InChiKey: OWZKIBRJGBBVJG-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  56.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3S)-3-tert-butoxy-1-hydroxypyrrolidine-2-carbonitrile 在 盐酸 、 5% Pd(OH)2/C 、 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、15.2 MPa 条件下， 反应 6.0h， 以100%的产率得到(2R,3S)-2-(aminomethyl)-3-hydroxypyrrolidine dihydrochloride
  参考文献：
  名称：

  环硝酮亲核添加到亚氨基环醇的过程中——DMDP、6-脱氧-DMDP、DAB-1、CYB-3、油桃和Radicamine B的全合成

  摘要：

  对衍生自 L-苹果酸和 D-阿拉伯糖的环状硝酮的高度非对映选择性亲核加成已用于构建对映异构纯的多羟基化吡咯烷。所采用的合成策略基于涉及羟胺/硝酮对的氧化/还原协议，并演示了试剂和底物衍生立体控制的使用。在大多数情况下，反应以完全非对映选择性和定量收率发生，无需纯化。通过这种策略，已经制备了具有丰富构型多样性的 2-(羟甲基)-、2-(氨基甲基)-和 2-芳基取代的多羟基吡咯烷。适当的底物和试剂的使用允许接近 DMDP、6-脱氧-DMDP、DAB-1、CYB-3、油桃和雷卡胺 B。

  DOI：

  10.1002/ejoc.200800098
• 作为产物：
  描述：

  (4S)-4-tert-butoxy-3,4-dihydro-2H-pyrrole 1-oxide 在 柠檬酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 17.0h， 生成 (2R,3S)-3-tert-butoxy-1-hydroxypyrrolidine-2-carbonitrile
  参考文献：
  名称：

  A comparative study of the stereoselective addition of trimethylsilyl cyanide and diethylaluminum cyanide to chiral cyclic nitrones

  摘要：

  The mild cyanating agent trimethylsilyl cyanide adds with total stereo selectivity to alpha-alkoxy cyclic nitrones to afford the corresponding trans-hydroxyaminonitriles. The addition of Lewis acids to precomplexing the nitrones does not affect the stereoselectivity of these additions significantly. In all of the cases examined, excellent yields of diastereomerically homogeneous products were obtained. On the other hand, the use of diethylaluminum cyanide as cyanating agent leads to low diastereoselectivities. Both NMR studies and theoretical calculations show that whereas the addition of trimethylsilyl cyanide takes place through a concerted mechanism, in the addition of diethylaluminum cyanide, a complex is formed prior to the intramolecular delivery of the cyanide ion. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00832-7

文献信息

• A comparative study of the stereoselective addition of trimethylsilyl cyanide and diethylaluminum cyanide to chiral cyclic nitrones
  作者：Pedro Merino、Tomas Tejero、Julia Revuelta、Pilar Romero、Stefano Cicchi、Vanni Mannucci、Alberto Brandi、Andrea Goti

  DOI：10.1016/s0957-4166(02)00832-7

  日期：2003.2

  The mild cyanating agent trimethylsilyl cyanide adds with total stereo selectivity to alpha-alkoxy cyclic nitrones to afford the corresponding trans-hydroxyaminonitriles. The addition of Lewis acids to precomplexing the nitrones does not affect the stereoselectivity of these additions significantly. In all of the cases examined, excellent yields of diastereomerically homogeneous products were obtained. On the other hand, the use of diethylaluminum cyanide as cyanating agent leads to low diastereoselectivities. Both NMR studies and theoretical calculations show that whereas the addition of trimethylsilyl cyanide takes place through a concerted mechanism, in the addition of diethylaluminum cyanide, a complex is formed prior to the intramolecular delivery of the cyanide ion. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Nucleophilic Additions to Cyclic Nitrones en Route to Iminocyclitols – Total Syntheses of DMDP, 6-deoxy-DMDP, DAB-1, CYB-3, Nectrisine, and Radicamine B
  作者：Pedro Merino、Ignacio Delso、Tomás Tejero、Francesca Cardona、Marco Marradi、Enrico Faggi、Camilla Parmeggiani、Andrea Goti

  DOI：10.1002/ejoc.200800098

  日期：2008.6

  with total diastereoselectivity and in quantitative yield, with no purification being necessary. By this strategy, 2-(hydroxymethyl)-, 2-(aminomethyl)-, and 2-aryl-substituted polyhydroxylated pyrrolidines have been prepared with abundant configurational diversity. The use of appropriate substrates and reagents allowed for approaches to DMDP, 6-deoxy-DMDP, DAB-1, CYB-3, nectrisine and radicamine B. Several

  对衍生自 L-苹果酸和 D-阿拉伯糖的环状硝酮的高度非对映选择性亲核加成已用于构建对映异构纯的多羟基化吡咯烷。所采用的合成策略基于涉及羟胺/硝酮对的氧化/还原协议，并演示了试剂和底物衍生立体控制的使用。在大多数情况下，反应以完全非对映选择性和定量收率发生，无需纯化。通过这种策略，已经制备了具有丰富构型多样性的 2-(羟甲基)-、2-(氨基甲基)-和 2-芳基取代的多羟基吡咯烷。适当的底物和试剂的使用允许接近 DMDP、6-脱氧-DMDP、DAB-1、CYB-3、油桃和雷卡胺 B。