N-benzyl-2-(3-chlorophenyl)-2-oxoacetamide | 190433-54-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-benzyl-2-(3-chlorophenyl)-2-oxoacetamide
• CAS: 190433-54-6
• 化学式: C₁₅H₁₂ClNO₂
• 分子量: 273.719
• InChiKey: JGRYEYVJFWCNOM-UHFFFAOYSA-N

物化性质

• 密度：
  1.266±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-benzyl-2-(3-chlorophenyl)-2-oxoacetamide 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 2-(benzylamino)-1-(3-chlorophenyl)-2-oxoethyl methanesulfonate
  参考文献：
  名称：

  在CONH基团存在下用芳基硼酸作为亲核剂的立体定向亲核取代

  摘要：

  用芳基硼酸作为亲核试剂首次实现了立体特异性亲核取代。手性α-芳基-α-甲基化乙酰胺和芳基硼酸之间的这种无过渡金属偶联使人们能够获得一系列具有出色对映选择性和中等至良好收率的手性α，α-二芳基乙酰胺。事实证明，CONH功能对于桥接反应物和促进反应至关重要。使用此方法成功完成了大麻素CB 1受体配体，抗抑郁药（S）-双氯芬素和抑制剂implitapide的关键手性构建体的高效合成。

  DOI：

  10.1002/anie.201712829
• 作为产物：
  描述：

  (3-chlorophenyl)magnesium bromide 生成 N-benzyl-2-(3-chlorophenyl)-2-oxoacetamide
  参考文献：
  名称：

  Asymmetric hydrogenation of α-keto acid derivatives by rhodium-}amidophosphine-phosphinite{ catalysts

  摘要：

  The enantioselective hydrogenation of several alpha-keto esters (3a-f, 5a-j), alpha-keto amides (7a-e) and isatine derivatives (9a-d) with a set of four representative neutral homogeneous rhodium-amidophosphine-phosphinite catalysts has been investigated. Trifluoroacetato-Rh-AMPP catalytic precursors promoted the rapid, efficient synthesis of aliphatic oc-hydroxy esters 4a-f in moderate to high enantioselectivities (66-95% ee), in contrast to most aromatic alpha-hydroxy esters 6a-j (8-81% ee). Best enantioselectivities for alpha-hydroxy amides 8a-e (85-95% ee) and dioxindoles 10a-d (80-94% ee) were obtained with chloro-Rh-AMPP precursors. It is proposed that, contrary to alpha-keto amides, alpha-keto esters do not chelate onto the rhodium center and that, in such circumstances, the asymmetric induction is mainly controlled by the steric hindrance around the C=O function. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00078-5

文献信息

• Enantioselective Iridium-Catalyzed Hydrogenation of α-Keto Amides to α-Hydroxy Amides
  作者：Guoxian Gu、Tilong Yang、Ouran Yu、Hua Qian、Jiang Wang、Jialin Wen、Li Dang、Xumu Zhang

  DOI：10.1021/acs.orglett.7b02912

  日期：2017.11.3

  A highly enantioselective iridium-catalyzed hydrogenation of α-keto amides to form α-hydroxy amides has been achieved with excellent results (up to >99% conversion and up to >99% ee, TON up to 100 000). As an example, this protocol was applied to the synthesis of (S)-4-(2-amino-1-hydroxyethyl)benzene-1,2-diol, the enantiomer of norepinephrine, which is widely used as an injectable drug for the treatment

  已经实现了高度对映选择性的铱催化的α-酮酰胺的氢化反应，形成α-羟基酰胺，具有优异的结果（转化率最高> 99％，ee最高> 99％，TON最高100000）。例如，该方案适用于去甲肾上腺素的对映异构体（S）-4-（2-氨基-1-羟乙基）苯-1,2-二醇的合成，该化合物被广泛用作严重低血压的治疗。还进行了密度泛函理论（DFT）计算以揭示反应机理。
• 催化前手性α-酮酰胺合成手性α-羟基酰胺的方法
  申请人：凯特立斯（深圳）科技有限公司

  公开号：CN107417562A

  公开（公告）日：2017-12-01

  本发明提供了一种全新制备手性α‑羟基酰胺的方法，通过使用新型的三齿氮膦配体对具有前手性的α‑酮酰胺进行不对称氢化反应制备一系列的手性α‑羟基酰胺化合物，方法包括：在氢气氛围下，在催化剂的存在下，加入前手性α‑酮酰胺和碱进行不对称氢化反应，得到手性α‑羟基酰胺；所述催化剂是由金属铱盐与手性配体络合得到。所述方法所使用的配体容易合成，反应具有高对映选择性、高收率、高转化数的特点，绝大多数底物在催化剂用量万分之一的情况下取得99％以上的转化率和97％‑99％以上的ee值，最高转化数达到100000，具有极高的工业化价值。
• Synthesis of α-Ketoamides from β-Ketonitriles and Primary Amines: A Catalyst-Free Oxidative Decyanation-Amidation Reaction
  作者：Ya-Kai Zhang、Bin Wang

  DOI：10.1002/ejoc.201900900

  日期：2019.9.8

  A catalyst‐free oxidative decyanation–amidation reaction is developed for the synthesis of α‐ketoamides using β‐ketonitriles, primary amines, and hydrogen peroxide sodium carbonate adduct (Na2CO3·1.5H2O2). This method is a valuable and simple strategy for the decyanation reaction.

  使用β-乙腈，伯胺和过氧化氢碳酸钠加合物（Na 2 CO 3 · 1.5H 2 O 2）开发了无催化剂的氧化脱氰-酰胺化反应，用于合成α-酮酰胺。该方法是用于脱氰反应的有价值且简单的策略。
• Stereospecific Nucleophilic Substitution with Arylboronic Acids as Nucleophiles in the Presence of a CONH Group
  作者：Duanshuai Tian、Chengxi Li、Guoxian Gu、Henian Peng、Xumu Zhang、Wenjun Tang

  DOI：10.1002/anie.201712829

  日期：2018.6.11

  first time with arylboronic acids as nucleophiles. This transition‐metal‐free coupling between chiral α‐aryl‐α‐mesylated acetamides and arylboronic acids provided access to a series of chiral α,α‐diaryl acetamides with excellent enantioselectivity and moderate to good yields. The CONH functionality proved to be crucial for bridging the reactants and promoting the reaction. Efficient syntheses of a cannabinoid

  用芳基硼酸作为亲核试剂首次实现了立体特异性亲核取代。手性α-芳基-α-甲基化乙酰胺和芳基硼酸之间的这种无过渡金属偶联使人们能够获得一系列具有出色对映选择性和中等至良好收率的手性α，α-二芳基乙酰胺。事实证明，CONH功能对于桥接反应物和促进反应至关重要。使用此方法成功完成了大麻素CB 1受体配体，抗抑郁药（S）-双氯芬素和抑制剂implitapide的关键手性构建体的高效合成。
• Asymmetric hydrogenation of α-keto acid derivatives by rhodium-}amidophosphine-phosphinite{ catalysts
  作者：Jean-François Carpentier、André Mortreux

  DOI：10.1016/s0957-4166(97)00078-5

  日期：1997.4

  The enantioselective hydrogenation of several alpha-keto esters (3a-f, 5a-j), alpha-keto amides (7a-e) and isatine derivatives (9a-d) with a set of four representative neutral homogeneous rhodium-amidophosphine-phosphinite catalysts has been investigated. Trifluoroacetato-Rh-AMPP catalytic precursors promoted the rapid, efficient synthesis of aliphatic oc-hydroxy esters 4a-f in moderate to high enantioselectivities (66-95% ee), in contrast to most aromatic alpha-hydroxy esters 6a-j (8-81% ee). Best enantioselectivities for alpha-hydroxy amides 8a-e (85-95% ee) and dioxindoles 10a-d (80-94% ee) were obtained with chloro-Rh-AMPP precursors. It is proposed that, contrary to alpha-keto amides, alpha-keto esters do not chelate onto the rhodium center and that, in such circumstances, the asymmetric induction is mainly controlled by the steric hindrance around the C=O function. (C) 1997 Elsevier Science Ltd.