2-cyano-N-methoxy-N-methylacetamide | 353237-65-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-cyano-N-methoxy-N-methylacetamide
• CAS: 353237-65-7
• 化学式: C₅H₈N₂O₂
• 分子量: 128.131
• InChiKey: LVFHKNRQGPZGGE-UHFFFAOYSA-N

物化性质

• 沸点：
  190.9±42.0 °C(Predicted)
• 密度：
  1.112±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 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：
  53.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-cyano-N-methoxy-N-methylacetamide 在 吡啶 、 triflic azide 作用下， 以 正己烷 、 乙腈 为溶剂， 反应 24.0h， 生成 2-cyano-2-diazo-N-methyl-N-methoxyacetamide
  参考文献：
  名称：

  供体-受体和双受体重氮试剂由烯丙酸酯催化不对称合成亚烷基环丙烷

  摘要：

  手性 ACP：描述了由缺电子丙二烯催化不对称合成亚烷基环丙烷。该方法使用供体-受体或双受体重氮试剂，由手性铑络合物催化，以高产率提供相应的 ACP，并具有出色的非对映选择性和对映选择性。

  DOI：

  10.1002/chem.202201438
• 作为产物：
  描述：

  N^α-formyl-N-methoxy-N-methyl-2-aminoacetamide 在 三乙胺 、 三氯氧磷 作用下， 以 四氢呋喃 为溶剂， 生成 2-cyano-N-methoxy-N-methylacetamide
  参考文献：
  名称：

  Gold(I)-Catalyzed Asymmetric Aldol Reaction of N-Methoxy-N-methyl-.alpha.-isocyanoacetamide (.alpha.-Isocyano Weinreb Amide). An Efficient Synthesis of Optically Active .beta.-Hydroxy .alpha.-Amino Aldehydes and Ketones

  摘要：

  Asymmetric aldol reaction of N-methoxy-N-methyl-alpha-isocyanoacetamide (alpha-isocyano Weinreb amide) with aldehydes [RCHO: R = Ph, Me, i-Pr, (E)-MeCH=CH, (E)-BnOCH(2)CH=CH] in the presence of a gold(I) catalyst prepared in situ from [Au(c-HexNC)(2)]BF4 and chiral ferrocenylphosphine ligand (R)-N-methyl-N-(2-morpholinoethyl)-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine gave high yields of optically active trans-5-alkyl-2-oxazoline-4-(N-methoxy-N-methylcarboxamides) with high diastereo- and enantioselectivities. The diastereoselectivities (trans:cis) and enantiomeric excesses of the trans-oxazolines for the reaction with 1 mol % of the catalyst are as follows: R = Ph, 97:3, 96% ee; R = Me, 95:5, 97% ee; R = i-Pr, 98:2, 97% ee; R = (E)-MeCH=CH, 97:3; 99% ee; (E)-BnOCH(2)CH=CH, 96:4, 95% ee. These optically active oxazolines were converted to N,O-protected beta-hydroxy-alpha-amino aldehydes and ketone in high yields. An N-protected alpha-amino aldehyde (R = Ph) lacking the beta-hydroxyl group was also obtained through the catalytic hydrogenolysis of the oxazoline.

  DOI：

  10.1021/jo00111a034

文献信息

• Enantioselective Cyclopropenation of Alkynes with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis
  作者：Xin Cui、Xue Xu、Hongjian Lu、Shifa Zhu、Lukasz Wojtas、X. Peter Zhang*

  DOI：10.1021/ja111334j

  日期：2011.3.16

  The cobalt(II) complex of a new D(2)-symmetric chiral porphyrin 3,5-diMes-ChenPhyrin, [Co(P2)], has been shown to be a highly effective chiral metalloradical catalyst for enantioselective cyclopropenation of alkynes with acceptor/acceptor-substituted diazo reagents, such as α-cyanodiazoacetamides and α-cyanodiazoacetates. The [Co(P2)]-mediated metalloradical cyclopropenation is suitable to a wide range

  新的 D(2)-对称手性卟啉 3,5-diMes-ChenPhyrin [Co(P2)] 的钴 (II) 配合物已被证明是一种高效的手性金属基催化剂，用于炔烃与受体的对映选择性环丙烯化/受体取代的重氮试剂，例如α-氰基重氮乙酰胺和α-氰基重氮乙酸盐。[Co(P2)] 介导的金属基环丙烯化反应适用于各种具有不同空间和电子性质的末端芳烃和相关共轭炔烃，以高产率提供相应的三取代环丙烯，对全碳四元立体中心具有出色的对映控制. 除了温和的反应条件外，用于环丙烯化的 Co(II) 基金属基催化还具有高度的官能团耐受性。
• ENANTIOSELECTIVE CYCLOPROPENATION OF ALKYNES
  申请人：Zhang X. Peter

  公开号：US20130030170A1

  公开（公告）日：2013-01-31

  The cobalt(II) complex of new D2-symmetric chiral porphyrin 3,5-DiMes-ChenPhyrin, [Co(P2)], has been shown to be a highly effective chiral metalloradical catalyst for enantioselective cyclopropenation of alkynes with acceptor/acceptor-substituted diazo reagents such as α-cyanodiazoacetamides and α-cyanodiazoacetates. The [Co(P2)]-mediated metalloradical cyclopropenation is suitable to a wide range of terminal aromatic and related conjugated alkynes with varied steric and electronic properties, providing the corresponding tri-substituted cyclopropenes in high yields with excellent enantiocontrol of the all-carbon quaternary stereogenic centers. In addition to mild reaction conditions, the Co(II)-based metalloradical catalysis for cyclopropenation features a high degree of functional group tolerance.

  新的D2对称手性卟啉3,5-DiMes-ChenPhyrin的钴（II）络合物[Co（P2）]已被证明是一种高效的手性金属自由基催化剂，用于炔烃与受体/受体取代重氮试剂（如α-氰基重氮乙酰胺和α-氰基重氮乙酸酯）的对映选择性环丙烯化反应。[Co（P2）]介导的金属自由基环丙烯化适用于范围广泛的末端芳香烃和相关共轭炔烃，具有不同的立体和电子性质，可提供相应的三取代环丙烯烃，收率高，对所有碳四取代立体中心的对映选择性控制良好。除了温和的反应条件外，基于Co（II）的金属自由基催化环丙烯化具有高度的官能团容忍性。
• Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes
  作者：Daniel T. Ziegler、Lorena Riesgo、Takuya Ikeda、Yuji Fujiwara、Gregory C. Fu

  DOI：10.1002/anie.201405854

  日期：2014.11.24

  fully substituted stereocenter [either all‐carbon or heteroatom‐substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four‐carbon coupling partner is not the turnover‐limiting step of the catalytic cycle.

  由于环戊烷亚基在生物活性化合物中频繁出现，开发有效的催化不对称合成方法是一个重要目标。本文介绍了一个新的手性亲核催化剂家族，联苯衍生的膦，我们将它们应用于有用的 [4+1] 环化的对映选择性变体。可以使用一系列单碳偶联伙伴，从而产生带有完全取代立体中心的环戊烯 [全碳或杂原子取代（硫和磷）]。环戊烷环其他四个位置的立体中心也可以以良好的立体选择性引入。
• Study of the Chemoselectivity of Grignard Reagent Addition to Substrates Containing Both Nitrile and Weinreb Amide Functionalities
  作者：Kommidi Harikrishna、Ananya Rakshit、Indrapal Singh Aidhen

  DOI：10.1002/ejoc.201300622

  日期：2013.8

  Several substrates containing both cyano and Weinreb amide functionalities have been synthesized to study the chemoselectivity of their reactions with organomagnesium bromides (ArMgBr and RMgBr). Excellent chemoselectivity towards the Weinreb amide was observed in most cases, even in the presence of excess Grignard reagent, affording cyano ketones in good-to-excellent yields.

  已经合成了几种含有氰基和 Weinreb 酰胺官能团的底物，以研究它们与有机溴化镁（ArMgBr 和 RMgBr）反应的化学选择性。在大多数情况下观察到对 Weinreb 酰胺的优异化学选择性，即使在过量格氏试剂存在的情况下，也能以良好到优异的产率提供氰基酮。
• Sawamura Masaya, Nakayama Yuki, Kato Tomoki, Ito Yoshihiko, J. Org. Chem, 60 (1995) N 6, S 1727-1732
  作者：Sawamura Masaya, Nakayama Yuki, Kato Tomoki, Ito Yoshihiko

  DOI：——

  日期：——