3-methyl-2-nitro-3-buten-1-ol | 134916-27-1

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 3-methyl-2-nitro-3-buten-1-ol
• 英文别名: 3-methyl-2-nitro-but-3-en-1-ol；3-Methyl-2-nitrobut-3-en-1-ol
• CAS: 134916-27-1
• 化学式: C₅H₉NO₃
• 分子量: 131.131
• InChiKey: DKLCCTQRVLJMJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-methyl-2-nitro-3-buten-1-ol 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 6-ethoxy-3a-prop-1-en-2-yl-3,4,5,6-tetrahydro-2H-[1,2]oxazolo[2,3-b]oxazine-2-carbonitrile
  参考文献：
  名称：

  3-取代的-2-硝基-1,3-二烯的生成和环加成反应。

  摘要：

  已经开发了两种用于区域特异性制备3-取代的-2-硝基-1，3-二烯的方法。已经研究了原位生成的二烯的环加成化学。

  DOI：

  10.1016/s0040-4039(00)74370-x
• 作为产物：
  描述：

  2-isopropenyl-2-nitro-propane-1,3-diol 在 sodium ethanolate 作用下， 生成 3-methyl-2-nitro-3-buten-1-ol
  参考文献：
  名称：

  Buckley; Charlish, Journal of the Chemical Society, 1947, p. 1473

  摘要：

  DOI：

文献信息

• A new enantioselective route to kainoids: application to the formal synthesis of (–)-α-kainic acid
  作者：Achille Barco、Simonetta Benetti、Gian P. Pollini、Giampiero Spalluto、Vinicio Zanirato

  DOI：10.1039/c39910000390

  日期：——

  The enantioselective synthesis of a 2,3,4-trisubstituted pyrrolidine featuring the kainoid C-2, C-3 trans, C-3, C-4 cis arrangement of substituents has been accomplished through a tandem Michael reaction strategy involving 2-nitro-3-methylbuta-1,3-diene as electrophilic alkene, the removable electron-withdrawing group acting as a template for control of the stereochemistry of the cyclization, together with a secondary benzylamine incorporating a chiral centre at the carbon bearing the nitrogen nucleophile and an appropriate α,β-unsaturated acceptor able to trap the initially formed nitronate.

  通过以 2-硝基-3-甲基丁-1,3-二烯为亲电烯烃的串联迈克尔反应策略，完成了一种 2,3,4-三取代吡咯烷的对映选择性合成，该吡咯烷具有凯氏 C-2、C-3 反式、C-3、C-4 顺式排列的取代基、可拆卸的抽电子基团可作为控制环化立体化学的模板，再加上在含氮亲核碳上含有手性中心的仲苄胺和能够捕获最初形成的硝酸酯的δ,δ-不饱和受体。
• A new approach to kainoids through tandem Michael reaction methodology: application to the enantioselective synthesis of (+)- and (-)-.alpha.-allokainic acid and to the formal synthesis of (-)-.alpha.-kainic acid
  作者：Achille Barco、Simonetta Benetti、Giampiero Spalluto、Alberto Casolari、Gian P. Pollini、Vinicio Zanirato

  DOI：10.1021/jo00049a040

  日期：1992.11

  A convergent, one-pot construction of functionalized pyrrolidine ring systems has been developed. The method is based on a tandem Michael reaction initiated by an intermolecular conjugate addition of a nitrogen nucleophile to an electrophilic olefin followed by trapping of the generated enolate by a built-in alpha,beta-unsaturated acceptor. After model studies verified the feasibility of the process and gave information about its stereochemical outcome, the strategy was successfully applied to kainoid synthesis. The construction of the basic pyrrolidine skeleton of all the members of the family requires coupling of a suitable electrophilic subunit with a common donor-acceptor fragment containing the nitrogen nucleophile. Thus, the enantioselective synthesis of (+)-alpha-allokainic acid (2) and the formal synthesis of its C-4 epimer (-)-alpha-kainic acid (1), have been accomplished using methyl vinyl ketone and 2-nitro-3-methyl-1,3-butadiene, respectively, as electrophilic partners of (S)-4-(benzylamino)-5-hydroxy-2-pentenoic acid ethyl ester (17), easily derived in six steps from D-serine. Although the acetyl group of methyl vinyl ketone is a logical precursor to the isopropenyl moiety of 2, the use of the nitrobutadiene is more appropriate for the synthesis of 1 because of the startling degree of control of the cyclization stereochemistry exerted by the nitro group.