c-cyclopropyl-N-methylnitrone | 86209-99-6

• 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: c-cyclopropyl-N-methylnitrone
• 英文别名: C-cyclopropyl-N-methyl nitrone；1-cyclopropyl-N-methylmethanimine oxide
• CAS: 86209-99-6
• 化学式: C₅H₉NO
• 分子量: 99.1326
• InChiKey: YWDOJNANUJWVCW-XQRVVYSFSA-N

物化性质

• 沸点：
  277.8±7.0 °C(Predicted)
• 密度：
  1.125±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  c-cyclopropyl-N-methylnitrone 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 5.0h， 生成 3-cyclopropyl-2-methyl-isoxazolidine-4-sulfonic acid allylamide
  参考文献：
  名称：

  Synthesis of Functionalized Sulfonamides via 1,3-Dipolar Cycloaddition of Pentafluorophenyl Vinylsulfonate

  摘要：

  [GRAPHICS]An efficient intermolecular 1,3-dipolar cycloaddition of a variety of nitrones to pentafluorophenyl (PFP) vinylsulfonate is described. The transformation produces stable "reversed" cycloadducts of unprecedented stereo- and regioselectivity. Subsequent amine displacement of the PFP moiety furnished functionalized sulfonamide products in good yields.

  DOI：

  10.1021/ol0347388
• 作为产物：
  描述：

  N-甲基羟胺 、 环丙甲醛 在 盐酸 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 c-cyclopropyl-N-methylnitrone
  参考文献：
  名称：

  Synthesis of Functionalized Sulfonamides via 1,3-Dipolar Cycloaddition of Pentafluorophenyl Vinylsulfonate

  摘要：

  [GRAPHICS]An efficient intermolecular 1,3-dipolar cycloaddition of a variety of nitrones to pentafluorophenyl (PFP) vinylsulfonate is described. The transformation produces stable "reversed" cycloadducts of unprecedented stereo- and regioselectivity. Subsequent amine displacement of the PFP moiety furnished functionalized sulfonamide products in good yields.

  DOI：

  10.1021/ol0347388

文献信息

• A new version of the reverse-Cope elimination initiated by the nucleophilic addition of allylamines to nitrones: a synthesis of vicinal diamines
  作者：Michael B. Gravestock、David W. Knight、K. M. Abdul Malik、Steven R. Thornton

  DOI：10.1039/b003959o

  日期：——

  are successful, giving the trans-oxadiazinanes 24, 33 and the stereoisomers 38 and 39 from linalylamine 37, but only when the terminus of the allylamine is unsubstituted are the reactions efficient. A range of N-alkylallylamines 43, 45, 47 and 49, however, react smoothly with nitrone 8, as competing imine formation is precluded. Various mechanistic aspects are discussed, along with the effects of aryl

  尝试在与被保护的烯丙胺6进行对映选择性[1,3]偶极环加成反应中使用糖衍生的硝酮1只是部分成功，得到了预期加合物的混合物7。但是，硝酮1和未保护的烯丙胺11之间的反应遵循不同的途径，涉及通过胺，反向应对 环化和Meisenheimer重排导致1,2,5- oxadiazinanes 12和13。与类似的反应苯甲醛衍生的硝酮8是成功的，赋予反-oxadiazinanes 24，33和立体异构体38和39从芳基胺 如图37所示，但是只有当烯丙基胺的末端未被取代时，反应才有效。的范围Ñ -alkylallylamines 43，45，47和49，但是，与硝酮顺利反应8，如竞争性亚胺排除形成。讨论了各种机械方面，以及以下方面的影响：芳基在N-苄基烯丙胺57中和在硝酮8的4-位（59）处的取代基，没有发现可以提高总反应速率的取代基。最初的恶二嗪酮可用作氨基羟胺69和邻位的前体二胺衍生物70。
• Reverse-Cope cyclisations of thiahydroxylamines derived from the addition of allylic thiols to nitrones: Syntheses of 1,3-thiazolidine-N-oxides and 1,5,2-oxathiazinanes
  作者：Michael P Coogan、Michael B Gravestock、David W Knight、Steven R Thornton

  DOI：10.1016/s0040-4039(97)10244-1

  日期：1997.12

  Allylthiols 7 react as nucleophiles with nitrones 8 to give intermediate thiahydroxylamines which undergo reverse-Cope cyclisations to provide 1,3-thiazolidine-N-oxides 9; in the case of derivatives of C-phenyl nitrone, thermolysis results in smooth Meisenheimer rearrangement leading to the 1,5,2-oxathiazinane 14.

  烯丙基硫醇7作为亲核试剂与硝酮8反应，生成中间体噻羟胺，将其进行反向Cope环化反应以提供1,3-噻唑烷-N-氧化物9；在C-苯基硝酮的衍生物的情况下，热分解导致平滑的Meisenheimer重排，从而导致1,5,2-氧杂噻嗪烷14。
• Organocatalysts Promote Enantioselective 1,3-Dipolar Cycloadditions of Nitrones with 1-Cycloalkene-1-carboxaldehydes
  作者：Staffan Karlsson、Hans-Erik Högberg

  DOI：10.1002/ejoc.200300172

  日期：2003.8

  In the presence of enantiopure organocatalysts, 1-cycloalkene-1-carboxaldehydes and various nitrones furnished fused isoxazolidines. Thus, some chiral pyrrolidinium salts catalyzed the formation of such cycloadducts in high diastereo- and enantioselectivity (up to 92% ee). The predominant diastereomer, the exo one, was mostly obtained in excellent diastereoselectivity (> 99:1 dr). Furthermore, after

  在对映体纯有机催化剂存在下，1-环烯烃-1-甲醛和各种硝酮提供稠合异恶唑烷。因此，一些手性吡咯烷盐以高非对映选择性和对映选择性（高达 92% ee）催化此类环加合物的形成。主要的非对映异构体，即外向异构体，主要以优异的非对映选择性 (> 99:1 dr) 获得。此外，在环加合物之一重结晶后，得到对映体纯（> 99% ee）。确定环加合物之一的绝对构型。
• On the Characteristics of Reverse-Cope Cyclizations of Homoallylic Sulfoxide Nitrone Adducts: A Highly Stereoselective Route to Pyrrolidine-N-oxides
  作者：Jane R. Hanrahan、David W. Knight、Rhys Salter

  DOI：10.1055/s-2001-17444

  日期：——

  Lithiated homoallylic sulfoxides 4 add smoothly to a selection of aldonitrones to give largely single diastereoisomers of the unsaturated hydroxylamines 5 which undergo reverse Cope cyclizations to give the highly substituted pyrrolidine-N-oxides 6 in a stereocontrolled manner.

  锂化高烯丙基亚砜4顺利地添加到一系列醛硝酮中，得到不饱和羟胺5的大部分单一非对映异构体，其经历反向Cope环化，以立体控制的方式得到高度取代的吡咯烷-N-氧化物6。
• Factors influencing the reverse-Cope approach to 1,2,5-oxadiazinanes from allylamines and nitrones: Optimization of a new vicinal diamine synthesis
  作者：Kathryn E. Bell、Michael P. Coogan、Michael B. Gravestock、David W. Knight、Steven R. Thornton

  DOI：10.1016/s0040-4039(97)10243-x

  日期：1997.12

  Nitrones generated from formaldehyde and N-alkyl-hydroxylamines are particularly suitable reactants in tandem reverse-Cope-Meisenheimer reactions leading to oxadiazinanes and thence N-hydroxydiamines and vicinal diamines, front allylamines. (C) 1997 Elsevier Science Ltd.