(Z)-N,2-dimethylpropan-1-imine oxide | 103558-97-0

• 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: (Z)-N,2-dimethylpropan-1-imine oxide
• 英文别名: Mldhbthlfchraa-xqrvvysfsa-；N,2-dimethylpropan-1-imine oxide
• CAS: 103558-97-0
• 化学式: C₅H₁₁NO
• 分子量: 101.148
• InChiKey: MLDHBTHLFCHRAA-XQRVVYSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• 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：

  (Z)-N,2-dimethylpropan-1-imine oxide 在 正丁基锂 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 78.25h， 生成
  参考文献：
  名称：

  A new, stereoselective approach to pyrrolidine-N-oxides by sequential condensation of sulfones with nitrones and reverse-cope elimination

  摘要：

  Lithiosulfones 10 condense smoothly and highly stereoselectively with nitrones 11 to give unsaturated hydroxylamines 12 which undergo reverse-Cope cyclisations at varying rates leading to pyrrolidine-N-oxidies 13 and 14; the former isomerized slowly to diastereoisomers 20. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)10245-3
• 作为产物：
  描述：

  N-甲基羟胺 、 异丁醛 在 magnesium sulfate 作用下， 以 氯仿 为溶剂， 反应 12.0h， 以90%的产率得到(Z)-N,2-dimethylpropan-1-imine oxide
  参考文献：
  名称：

  Steric effects on regioselectivity in 1.3-Dipolar cycloaddition of C,N-dialyl nitrones with acceptor-substituted alkynes

  摘要：

  The 1.3 dipolar cycloaddition of alkynes 4-6 with acyclic nitrones 1-3, 23 and 24 as well as with cyclic nitrones 27 is studied. As was found for the reaction of the aldonitrones 1-3 an increased portion of 5-regioisomers is formed with increasing steric demand of either of the two substituents, the C-alkyl substituent R2 and the N-alkyl substituent R1. Thus the conclusion is drawn that cycloaddition of 1-3 proceeds not only via transition states arising from Z-nitrones but also via transition states developing from E-nitrones, although in the ground-state the Z-isomer is favored to a considerable extent. In this context steric destabilization of the transition states is discussed qualitatively.

  DOI：

  10.1016/s0040-4020(01)88127-8

文献信息

• Asymmetric “Acetylenic” [3+2] Cycloaddition of Nitrones Catalyzed by Cationic Chiral Pd^II Lewis Acid
  作者：Kazuya Honda、Koichi Mikami

  DOI：10.1002/asia.201801016

  日期：2018.10.4

  Highly enantioselective [3+2] cycloaddition of ynones and nitrones has been developed. Very bulky ligand, DTBM‐SEGPHOS, was used for an effective asymmetric induction over distal reaction centers on the linear ynone dipolarophile and for prevention of PdII catalyst deactivation by coordination of the nitrones. The reaction has wide scope of substrates in both ynones and nitrones.

  已经开发出对映体和硝酮的高度对映选择性的[3 + 2]环加成反应。很大体积的配体DTBM-SEGPHOS用于在线性乙炔双极性亲和体的远端反应中心进行有效的不对称诱导，并通过硝酮的配位防止Pd II催化剂失活。该反应在炔酮和硝酮中具有广泛的底物范围。
• Photoredox-Catalyzed Decarboxylative Cross-Coupling of α-Amino Acids with Nitrones
  作者：Heng-Hui Li、Jia-Qi Li、Xiao Zheng、Pei-Qiang Huang

  DOI：10.1021/acs.orglett.0c04101

  日期：2021.2.5

  A decarboxylative cross-coupling reaction of α-amino acids with nitrones via visible-light-induced photoredox catalysis has been established for easy access to β-amino hydroxylamines and vicinal diamines with structural diversity, which is featured with simple operation, mild conditions, readily available α-amino acids, and a broad scope of nitrone substrates. The application of this protocol can furnish

  建立了α-氨基酸与硝酮通过可见光诱导的光氧化还原催化的脱羧交叉偶联反应，易于获得具有结构多样性的β-氨基羟胺和邻二胺，具有操作简单、条件温和、容易获得的特点。可用的α-氨基酸，以及广泛的硝酮底物。该协议的应用可以为一些有价值的含有连二胺的分子提供有效的合成策略。
• Formation of cycloadducts with trans-configurated ester groups from nitrones and dimethyl maleate
  作者：Hans Günter Aurich、Gerlinde Frenzen、Markus G. Rohr

  DOI：10.1016/s0040-4020(01)90471-5

  日期：——

  there is no clue for either a non-concerted reaction course or a subsequent conversion of the cis-products to trans-product in general. Rather conversion of dimethyl maleate to dimethyl fumarate seems to be responsible for the formation of the trans-substituted cycloadducts. This conversion can be induced by small quantities of N-alkylhydroxylamine formed from slight decomposition of nitrones under the

  在1.3偶极环加成中，环状硝酮1c和非环状硝酮8a-h 12a b用马来酸二甲酯在回流的氯仿中，不仅形成了具有两个酯基的顺式构型的预期环加合物，而且还形成了具有反式构型的环加合物。该现象不仅限于氯仿，而且在极性溶剂如环己烷和正己烷中也观察到。但是，对于不确定的反应过程或随后的顺式产物向反式产物的转化，通常都没有任何线索。马来酸二甲酯向富马酸二甲酯的相反转化似乎是反式取代的环加合物形成的原因。在反应条件下，由硝酮的轻微分解形成的少量N-烷基羟胺，或由少量具有NOH部分的硝酮衍生物（如N-羟基烯胺互变异构体或硝酮二聚体）可以诱导这种转化。
• Lipase-catalyzed asymmetric synthesis of oxathiazinanones through dynamic covalent kinetic resolution
  作者：Lei Hu、Yan Zhang、Olof Ramström

  DOI：10.1039/c4ob00365a

  日期：——

  A domino addition–lactonization pathway has been applied to a dynamic covalent resolution protocol, leading to efficient oxathiazinanone formation as well as chiral discrimination. A new, double biocatalytic pathway has furthermore been proposed and evaluated where the initial product inhibition could be efficiently circumvented.

  多米诺加成-内酰胺化途径已应用于动态共价拆分方案，导致有效的草并噻嗪酮形成以及手性鉴别。此外，还提出了一种新的双重生物催化途径，并对其进行了评估，从而可以有效地规避最初的产物抑制作用。
• Diastereoselective synthesis of cis-2,5-disubstituted pyrrolidine N-oxides by the retro-Cope elimination
  作者：Mark C Bagley、Julie Tovey

  DOI：10.1016/s0040-4039(00)01964-x

  日期：2001.1

  Nitrones were reacted with 3-butenylmagnesium bromide to give alkenylhydroxylamines that were cyclised by retro-Cope elimination. Heating the diastereomeric mixtures of pyrrolidine N-oxides in the absence of solvent affected a highly diastereoselective isomerisation to provide the cis-2,5-disubstituted products in excellent yield. (C) 2000 Elsevier Science Ltd. All rights reserved.