4-acetyl-N-methoxy-N-methylbenzamide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-acetyl-N-methoxy-N-methylbenzamide
• 化学式: C₁₁H₁₃NO₃
• mdl: MFCD28165937
• 分子量: 207.229
• InChiKey: YTMCFAUSYHBYSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.272
• 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：

  4-acetyl-N-methoxy-N-methylbenzamide 在 Schwartz's reagent 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以91%的产率得到4-(1-hydroxyethyl)benzaldehyde
  参考文献：
  名称：

  Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp₂Zr(H)Cl:  Scope and Mechanistic Insight

  摘要：

  An investigation of the use of Cp2Zr(H)Cl (Schwartz's reagent) to reduce a variety of amides to the corresponding aldehydes under very mild reaction conditions and in high yields is reported. A range of tertiary amides, including Weinreb's amides, can be converted directly to the corresponding aldehydes with remarkable chemoselectivity. Primary and secondary amides proved to be viable substrates for reduction as well, although the yields were somewhat diminished as compared to the corresponding tertiary amides. Results from NMR experiments suggested the presence of a stable, 18-electron zirconacycle intermediate that presumably affords the aldehyde upon water or silica gel workup. A series of competition experiments revealed a preference of the reagent for substrates in which the lone pair of the nitrogen is electron releasing and thus more delocalized across the amide bond by resonance. This trend accounts for the observed excellent selectivity for tertiary amides versus esters. Experiments regarding the solvent dependence of the reaction suggested a kinetic profile similar to that postulated for the hydrozirconation of alkenes and alkynes. Addition of p-anisidine to the reaction intermediate resulted in the formation of the corresponding imine mimicking the addition of water that forms the aldehyde.

  DOI：

  10.1021/ja066362+
• 作为产物：
  描述：

  4-乙酰基苯甲酸 、 二甲羟胺盐酸盐 在 N-溴代丁二酰亚胺(NBS) 、 三苯基膦 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.25h， 以81%的产率得到4-acetyl-N-methoxy-N-methylbenzamide
  参考文献：
  名称：

  由羧酸直接合成各种酰化剂

  摘要：

  摘要描述了使用 PPh3/NBS 组合从芳香族、脂肪族羧酸和氨基酸直接合成酰化试剂，如 Weinreb 和 MAP 酰胺。介绍了在活性更高的醛和酮存在下，将羧酸基团化学选择性修饰成 Weinreb 酰胺。所有反应均在环境温度和空气中使用未干燥的商业级溶剂进行。此外，本方法可以在无惰性反应条件下以克规模进行。此外，7-氮杂吲哚啉酰胺助剂（用于催化不对称醛醇和曼尼希型反应），其行为类似于韦恩雷布酰胺，也在类似的反应条件下合成。图形概要

  DOI：

  10.1080/00397911.2020.1747631

文献信息

• Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds
  作者：Haining Wang、Xi-Jie Dai、Chao-Jun Li

  DOI：10.1038/nchem.2677

  日期：2017.4

  ruthenium catalyst and diphosphine ligand under mild conditions, delivering synthetically valuable secondary and tertiary alcohols in up to 98% yield. The unique chemoselectivity exhibited by carbonyl-derived carbanion equivalents is demonstrated by their tolerance to protic reaction media and good functional group compatibility. Enantioenriched tertiary alcohols can also be accessed with the aid of chiral

  有机金属试剂与羰基化合物的亲核加成反应用于碳-碳键的构建在现代化学中起着举足轻重的作用。但是，该反应对石油衍生的化学原料的依赖和化学计量的金属促使人们开发了许多碳负当量和催化金属替代品。在这里，我们表明，天然存在的羰基可以通过还原极性反转，用作潜在的烷基碳负离子当量，用于添加到羰基化合物中。这样的挑战钌催化剂和二膦配体在温和的条件下促进了反应活性，提供了合成有价值的仲醇和叔醇，收率高达98％。羰基衍生的碳负离子等同物表现出的独特的化学选择性是通过其对质子反应介质的耐受性和良好的官能团相容性来证明的。即使手性适度，也可以借助手性配体获得富含对映体的叔醇。预期这种羰基衍生的碳负当量在化学键形成中具有广泛的用途。
• Weinreb Amide Directed Versatile C−H Bond Functionalization under (η ⁵ ‐Pentamethylcyclopentadienyl)cobalt(III) Catalysis
  作者：Kentaro Kawai、Youka Bunno、Tatsuhiko Yoshino、Shigeki Matsunaga

  DOI：10.1002/chem.201801750

  日期：2018.7.17

  The (η5‐pentamethylcyclopentadienyl)cobalt(III) (Cp*CoIII)‐catalyzed C−H bond functionalization of aromatic, heteroaromatic, and α,β‐unsaturated Weinreb amides was explored. C−H allylation reactions with the use of allyl carbonate and a perfluoroalkene, oxidative alkenylation reactions with the use of ethyl acrylate, iodination reactions with the use of N‐iodosuccinimide, and amidation reactions with

  探索了(η 5 -五甲基环戊二烯基)钴 (III) (Cp*Co III )-催化的芳族、杂芳族和 α,β-不饱和 Weinreb 酰胺的 C-H 键官能化。Cp * Co ( CO)I 2在阳离子 Ag 盐和 AgOAc 存在下提供各种合成有用的结构单元。C−H 烯丙基化的机理研究表明，C−H 激活步骤决定速率并且几乎不可逆。
• Microwave-Assisted Synthesis of Weinreb and MAP Aryl Amides via Pd-Catalyzed Heck Aminocarbonylation Using Mo(CO)₆ or W(CO)₆
  作者：Anna Wiȩckowska、Rebecca Fransson、Luke R. Odell、Mats Larhed

  DOI：10.1021/jo102151u

  日期：2011.2.4

  A simple and expedient process for the Heck aminocarbonylative synthesis of Weinreb and MAP amide acylating agents, from aryl halides, is reported. This methodology utilizes solid sources of CO making it readily accessible to chemists working in small-scale laboratory applications.

  据报道，由芳基卤化物进行Weinreb和MAP酰胺酰化剂的Heck氨基羰基化合成的简便方法。这种方法利用了固体二氧化碳的来源，使小规模实验室应用中的化学家可以轻松获得二氧化碳。
• C−H Oxygenation Reactions Enabled by Dual Catalysis with Electrogenerated Hypervalent Iodine Species and Ruthenium Complexes
  作者：Leonardo Massignan、Xuefeng Tan、Tjark H. Meyer、Rositha Kuniyil、Antonis M. Messinis、Lutz Ackermann

  DOI：10.1002/anie.201914226

  日期：2020.2.17

  The catalytic generation of hypervalent iodine(III) reagents by anodic electrooxidation was orchestrated towards an unprecedented electrocatalytic C−H oxygenation of weakly coordinating aromatic amides and ketones. Thus, catalytic quantities of iodoarenes in concert with catalytic amounts of ruthenium(II) complexes set the stage for versatile C−H activations with ample scope and high functional group

  通过阳极电氧化催化生成高价碘（III）试剂，从而实现了对弱配位芳香族酰胺和酮的前所未有的电催化CH氧化。因此，催化量的碘代芳烃与催化量的钌（II）配合物协同作用，为具有广泛范围和高官能团耐受性的通用CH活化奠定了基础。通过实验和计算的详细机理研究证实了碘代芳烃作为电化学相关物种在CH-H氧化中的作用，其中电作为可持续的氧化剂，而分子氢作为唯一的副产物。在没有导向基团的情况下，对位选择性C–H氧合同样被证明是可行的。
• An Efficient synthesis of Weinreb amides and ketones via palladium nanoparticles on ZIF-8 catalysed carbonylative coupling
  作者：Tuan Thanh Dang、Anqi Chen、Abdul Majeed Seayad

  DOI：10.1039/c4ra04614e

  日期：——

  such as aminocarbonylation and Suzuki-carbonylation are reported using Pd nanoparticles supported on ZIF-8 for efficient and environmentally attractive synthesis of Weinreb amides and ketones from aryl bromides or iodides. The catalyst is air stable, offers high activity with very low palladium leaching and is recyclable. The presence of a phosphine ligand was required when aryl bromides were used as substrates

  据报道，使用负载在ZIF-8上的Pd纳米颗粒进行异质催化的羰基化偶联反应，例如氨基羰基化和Suzuki-羰基化，可从芳基溴化物或碘化物高效合成Weinreb酰胺和酮。该催化剂是空气稳定的，具有很高的活性，钯的浸出量极低，并且可回收利用。当使用芳基溴化物作为底物时，需要膦配体的存在，而当使用芳基碘化物时，则不需要配体。