N-Methoxy-N-methyl-α-oxohexaneamide | 141694-32-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-Methoxy-N-methyl-α-oxohexaneamide
• 英文别名: N-methoxy-N-methyl-2-oxohexanamide
• CAS: 141694-32-8
• 化学式: C₈H₁₅NO₃
• 分子量: 173.212
• InChiKey: DTSVFFQKIBJHHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-Methoxy-N-methyl-α-oxohexaneamide 在 甲醇 、 sodium tetrahydroborate 作用下， 生成 2-hydroxy-N-methoxy-N-methylhexanamide
  参考文献：
  名称：

  α-酮酰胺的不对称转移氢化；苹果酸二酰胺和α-羟基酰胺的高度对映选择性形成

  摘要：

  使用系留的 Ru/TsDPEN 催化剂在高 ee 下实现了 α-酮基-1,4-二酰胺的不对称转移氢化（ATH）。对衍生物的研究确定了导致产品中最高对映选择性的结构元素。α-酮酰胺还原产物已转化为一系列具有合成价值的衍生物。

  DOI：

  10.1021/acs.orglett.1c02830
• 作为产物：
  描述：

  正溴丁烷 、 N,N'-二甲氧基-N,N'-二甲基乙二酰二胺 在 碘 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 2.08h， 以0.653 g的产率得到N-Methoxy-N-methyl-α-oxohexaneamide
  参考文献：
  名称：

  α-酮酰胺的不对称转移氢化；苹果酸二酰胺和α-羟基酰胺的高度对映选择性形成

  摘要：

  使用系留的 Ru/TsDPEN 催化剂在高 ee 下实现了 α-酮基-1,4-二酰胺的不对称转移氢化（ATH）。对衍生物的研究确定了导致产品中最高对映选择性的结构元素。α-酮酰胺还原产物已转化为一系列具有合成价值的衍生物。

  DOI：

  10.1021/acs.orglett.1c02830

文献信息

• .alpha.-Keto Amides and 1,2-Diketones from N,N'-Dimethoxy-N,N'-dimethylethanediamide. A Synthetic and Mechanistic Investigation
  作者：Mukund P. Sibi、Mali Marvin、Rajiv Sharma

  DOI：10.1021/jo00121a021

  日期：1995.8

  N,N'-Dimethoxy-N,N'-dimethylethanediamide (1), a 1,2-dicarbonyl synthon prepared from oxalyl chloride, undergoes nucleophilic displacements with Grignard reagents to provide alpha-keto amides 2-12 in 28-90% yields. The synthon also undergoes double nucleophilic displacements with organolithium reagents to furnish symmetrical 1,2-diketones 15-23 in 15-84% yields. A mechanism accounting for all the products from the reaction of 1 with nucleophiles has been proposed. Several control experiments were carried out to support the proposed mechanism.
• N,N′-Dimethoxy-N,Nt́-Dimethylethanediamide: A Useful α-Oxo-N-Methoxy-N-Methylamide and 1,2-Diketone Synthon
  作者：Mukund P. Sibi、Rajiv Sharma、Kevin L. Paulson

  DOI：10.1016/0040-4039(92)88108-h

  日期：1992.4

  N,N'-Dimethoxy-N,N'-dimethylethanediamide on treatment with one to two equivalents of alkyl, aryl, and benzyl Grignard reagents provide alpha-oxo-N-methoxy-N-methylamides in good to excellent yields and on reaction with excess aryllithiums furnish moderate to good yields of symmetrical 1,2-diarylketones.
• Novel Synthesis of 2-Oxo-4-phenyl-3-butynoic Acid, a New Inhibitor and Alternate Substrate of Pyruvate Decarboxylase
  作者：Chingfan C. Chiu、Frank Jordan

  DOI：10.1021/jo00098a041

  日期：1994.9

  An improved method is reported for the synthesis of 2-oxo acids and is applied to the synthesis of 2-oxo-4-phenyl-3-butynoic acid. The compound is synthesized by reacting the N-methoxy-N-methylamide of monoethyloxalic acid with lithium phenylacetylide yielding ethyl 2-oxo-4-phenyl-3-butynoate (78% yield), followed by strictly pH-controlled hydrolysis to the free acid in nearly quantitative yield. The compound is shown to be a potent irreversible inhibitor of brewers' yeast pyruvate decarboxylase, in addition to producing both cis- and trans-cinnamic acids as products of turnover. The formation of these isomeric cinnamic acids can be rationalized if the thiamin diphosphate-bound alpha-carbanion/enamine intermediate resulting from decarboxylation is protonated at the side chain gamma carbon to form two diastereomeric allenols, whose tautomerization and hydrolysis lead to the two products.
• Chiu Chingfan C., Jordan Frank, J. Org. Chem, 59 (1994) N 19, S 5763-5766
  作者：Chiu Chingfan C., Jordan Frank

  DOI：——

  日期：——
• Asymmetric Transfer Hydrogenation of α-Keto Amides; Highly Enantioselective Formation of Malic Acid Diamides and α-Hydroxyamides
  作者：Shweta K. Gediya、Vijyesh K. Vyas、Guy J. Clarkson、Martin Wills

  DOI：10.1021/acs.orglett.1c02830

  日期：2021.10.15

  The asymmetric transfer hydrogenation (ATH) of α-keto-1,4-diamides using a tethered Ru/TsDPEN catalyst was achieved in high ee. Studies on derivatives identified the structural elements which lead to the highest enantioselectivities in the products. The α-keto-amide reduction products have been converted to a range of synthetically valuable derivatives.

  使用系留的 Ru/TsDPEN 催化剂在高 ee 下实现了 α-酮基-1,4-二酰胺的不对称转移氢化（ATH）。对衍生物的研究确定了导致产品中最高对映选择性的结构元素。α-酮酰胺还原产物已转化为一系列具有合成价值的衍生物。