N-Methyl-(2,2-dimethylpropylidene)amine N-oxide | 66251-86-3

• 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: N-Methyl-(2,2-dimethylpropylidene)amine N-oxide
• 英文别名: N-(2,2-dimethylpropylidene)methanamine oxide；(Z)-N,2,2-trimethylpropan-1-imine oxide；Xhbciemaskbfgw-alcczggfsa-；N,2,2-trimethylpropan-1-imine oxide
• CAS: 66251-86-3；127872-10-0
• 化学式: C₆H₁₃NO
• 分子量: 115.175
• InChiKey: XHBCIEMASKBFGW-ALCCZGGFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  N-Methyl-(2,2-dimethylpropylidene)amine N-oxide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 氘代氯仿 为溶剂， 反应 4.1h， 生成 (1R,2R,3R,5R)-3-Benzenesulfinyl-2-tert-butyl-1,5-dimethyl-pyrrolidine 1-oxide
  参考文献：
  名称：

  On the Characteristics of Reverse-Cope Cyclizations of Homoallylic Sulfoxide Nitrone Adducts: A Highly Stereoselective Route to Pyrrolidine-N-oxides

  摘要：

  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。

  DOI：

  10.1055/s-2001-17444
• 作为产物：
  描述：

  N-甲基羟胺 、 特戊醛 在 magnesium sulfate 作用下， 以 氯仿 为溶剂， 反应 12.0h， 以73%的产率得到N-Methyl-(2,2-dimethylpropylidene)amine N-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。
• 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。
• Trimethylsilyl trifluoromethanesulfonate promoted [3 + 2] dipolar cycloaddition of nitrones and silyl enol ethers: an efficient route to 5-siloxyisoxazolidines
  作者：Dilip D. Dhavale、Claudio Trombini

  DOI：10.1039/c39920001268

  日期：——

  The reaction of silyl enol ethers and nitrones, in the presence of trimethylsilyl trifluoromethanesulfonate, gives 5-siloxyisoxazolidines in excellent yield under fairly mild conditions.

  在三甲基甲硅烷基三氟甲磺酸酯的存在下，甲硅烷基烯醇醚和硝酮的反应在相当温和的条件下以优异的产率得到了5-甲硅烷氧基异恶唑烷。
• A Novel Nitrone Cycloaddition/Rearrangement
  作者：Bruce H. Toder、George B. Mullen、Vassil St. Georgiev

  DOI：10.1002/hlca.19900730119

  日期：1990.1.31

  Adamantanone-derived nitrone 4 and some other keto-nitrones, when reacted with aromatic and aliphatic aldehydes in refluxing toluene or tetrahydrofuran, formed the corresponding aldonitrones (Z)-10, the latter arising from the fragmentation of an initially formed 1,4,2-dioxazolidine 6 to adamantan-2-one and an oxaziridine intermediate 11, which then rearranges to (Z)-10.

  金刚烷酮衍生的硝酮4和其他一些酮-硝酮，当与芳族和脂族醛在回流的甲苯或四氢呋喃中反应，形成相应的aldonitrones（ż） - 10，后者从初始形成的碎片而产生1，4，2 -二恶唑烷6至金刚烷-2-酮和恶唑烷中间体11，然后将其重排为（Z）-10。
• Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane
  作者：Yao Xu、Hai‐Xiang Gao、Chengkai Pan、Yue Shi、Chi Zhang、Genping Huang、Chao Feng

  DOI：10.1002/anie.202310671

  日期：2023.10.26

  A radical type (3+3) cycloaddition of cyclopropane is realized with aryl cyclopropane and nitrone under photoredox catalysis in a highly regio- and diastereoselective manner. The reaction includes a stereospecific three-electron-type nucleophilic ring opening and a 6-endo-trig radical cyclization.

  在光氧化还原催化下，芳基环丙烷和硝酮以高度区域和非对映选择性的方式实现了环丙烷的自由基型(3+3)环加成。该反应包括立体特异性三电子型亲核开环和6-内三自由基环化。