4-methoxymethoxy-3,4-dihydro-2H-pyrrole 1-oxide | 532983-47-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: 4-methoxymethoxy-3,4-dihydro-2H-pyrrole 1-oxide
• 英文别名: (4S)-4-(methoxymethoxy)-1-oxido-3,4-dihydro-2H-pyrrol-1-ium
• CAS: 532983-47-4
• 化学式: C₆H₁₁NO₃
• 分子量: 145.158
• InChiKey: KQGUOWLVQOJBMT-LURJTMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  47.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-methoxymethoxy-3,4-dihydro-2H-pyrrole 1-oxide 在 三氟甲磺酸三甲基硅酯 、 柠檬酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.08h， 生成 (2R,3S)-1-hydroxy-3-(methoxymethoxy)pyrrolidine-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
• 作为产物：
  描述：

  (S)-1,4-di-O-mesyl-O-(methoxymethyl)-1,2,4-butanetriol 在 manganese(IV) oxide 、 盐酸羟胺 、 三乙胺 作用下， 以 氯仿 为溶剂， 反应 4.0h， 生成 4-methoxymethoxy-3,4-dihydro-2H-pyrrole 1-oxide
  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

• Tunable Diastereoselection of Biased Rigid Systems by Lewis Acid Induced Conformational Effects: A Rationalization of the Vinylation of Cyclic Nitrones En Route to Polyhydroxylated Pyrrolidines
  作者：Ignacio Delso、Eduardo Marca、Vanni Mannucci、Tomás Tejero、Andrea Goti、Pedro Merino

  DOI：10.1002/chem.201001608

  日期：2010.8.23

  biased rigid systems can be modulated by the action of Lewis acids. As an example, the stereoselectivity of the nucleophilic addition of vinyl magnesium bromide (VMB) to cyclic nitrones in the presence of diethylaluminum chloride (DEAC) shows a strong dependence on the temperature and the carbon substituent adjacent at the reaction center; it is remarkable that whereas a high selectivity is obtained

  可以通过路易斯酸的作用来调节除偏向刚性系统以外的反应中的非对面选择。例如，在氯化二乙基铝（DEAC）存在下，乙烯基溴化镁（VMB）与环状硝酮的亲核加成反应的立体选择性强烈依赖于温度和反应中心附近的碳取代基。值得注意的是，尽管在较高的温度下可获得高选择性，但在DEAC的存在下，在较低的温度下观察到了逆转反应的立体化学过程的趋势，只要吡咯烷环的C3处的取代基允许乙烯基的传递​​即可。部分。在此选择性的行为和不同的是归因于中间硝酮的高的构象障碍DEAC  VMB复杂。在−78°C下，对于被保护为O-甲基衍生物的硝酮的反应，选择性发生了明显的反转。本研究为亲核体向刚性系统（环状硝酮）的立体控制加成提供了合理化的方法。
• 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.