N-(4-methoxybenzoyl)methionine

• 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: N-(4-methoxybenzoyl)methionine
• 英文别名: 2-[(4-Methoxyphenyl)formamido]-4-(methylsulfanyl)butanoic acid；2-[(4-methoxybenzoyl)amino]-4-methylsulfanylbutanoic acid
• 化学式: C₁₃H₁₇NO₄S
• mdl: MFCD06356482
• 分子量: 283.348
• InChiKey: MNBUNUWZMJHWFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.384
• 拓扑面积：
  101
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-(4-methoxybenzoyl)methionine 在 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 生成 2-(4-methoxyphenyl)-4-(2-(methylthio)ethyl)oxazol-5-oxo-4,5-dihydrooxazole
  参考文献：
  名称：

  2-取代的 DMAP-N-氧化物作为酰基转移催化剂的合理设计：吖内酯的动态动力学拆分

  摘要：

  提出了一种新概念，即手性 2-取代 DMAP 转化为其 DMAP-N-氧化物可以显着提高催化活性，并且仍可用作酰基转移催化剂。一种由l-脯氨酰胺衍生的新型手性2-取代DMAP-N-氧化物被合理设计、简便合成并应用于吖内酯的动态动力学拆分。使用简单的甲醇作为亲核试剂，可以高产率（高达 98% 的产率）和对映选择性（高达 96% ee）生产各种 L-氨基酸衍生物。此外，还获得了α-氘标记的l-苯丙氨酸衍生物。实验和 DFT 计算表明，在 2-取代的 DMAP-N-氧化物中，氧原子充当亲核位点，NH 键充当 H 键供体。反应的高对映选择性受空间因素的控制，苯甲酸的加入通过参与氢键的构建降低了活化能。理论化学研究表明，只有充分考虑手性催化剂的攻击方向，才能得到正确的计算结果。这项工作为利用吡啶环的 C2 位置和开发手性 2-取代 DMAP-N-氧化物作为有效的酰基转移催化剂铺平了道路。

  DOI：

  10.1021/jacs.0c09075
• 作为产物：
  描述：

  DL-蛋氨酸 在 氯化亚砜 、 三乙胺 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 N-(4-methoxybenzoyl)methionine
  参考文献：
  名称：

  Regiodivergent Enantioselective γ-Additions of Oxazolones to 2,3-Butadienoates Catalyzed by Phosphines: Synthesis of α,α-Disubstituted α-Amino Acids and N,O-Acetal Derivatives

  摘要：

  Phosphine-catalyzed regiodivergent enantioselective C-2- and C-4-selective gamma-additions of oxazolones to 2,3-butadienoates have been developed. The C-4-selective gamma-addition of oxazolones occurred in a highly enantioselective manner when 2-aryl-4-alkyloxazol-5-(4H)-ones were employed as pronudeophiles. With the employment of 2-alkyl-4-aryloxazol-5-(4H)-ones as the donor, C-2-selective gamma-addition of oxazolones took place in a highly enantioselective manner. The C-4-selective adducts provided rapid access to optically enriched alpha,alpha-disubstituted alpha-amino acid derivatives, and the C-2-selective products led to facile synthesis of chiral N,O-acetals and gamma-lactols. Theoretical studies via DFT calculations suggested that the origin of the observed regioselectivity was due to the distortion energy that resulted from the interaction between the nudeophilic oxazolide and the electrophilic phosphonium intermediate.

  DOI：

  10.1021/jacs.5b10524

文献信息

• Rational Design of 2-Substituted DMAP-<i>N</i>-oxides as Acyl Transfer Catalysts: Dynamic Kinetic Resolution of Azlactones
  作者：Ming-Sheng Xie、Bin Huang、Ning Li、Yin Tian、Xiao-Xia Wu、Yun Deng、Gui-Rong Qu、Hai-Ming Guo

  DOI：10.1021/jacs.0c09075

  日期：2020.11.11

  A novel concept that conversion of chiral 2-substituted DMAP into its DMAP-N-oxide could significantly enhance the catalytic activity and still be used as an acyl transfer catalyst is presented. A new type of chiral 2-substituted DMAP-N-oxides, derived from l-prolinamides, has been rationally designed, facilely synthesized, and applied in the dynamic kinetic resolution of azlactones. Using simple MeOH

  提出了一种新概念，即手性 2-取代 DMAP 转化为其 DMAP-N-氧化物可以显着提高催化活性，并且仍可用作酰基转移催化剂。一种由l-脯氨酰胺衍生的新型手性2-取代DMAP-N-氧化物被合理设计、简便合成并应用于吖内酯的动态动力学拆分。使用简单的甲醇作为亲核试剂，可以高产率（高达 98% 的产率）和对映选择性（高达 96% ee）生产各种 L-氨基酸衍生物。此外，还获得了α-氘标记的l-苯丙氨酸衍生物。实验和 DFT 计算表明，在 2-取代的 DMAP-N-氧化物中，氧原子充当亲核位点，NH 键充当 H 键供体。反应的高对映选择性受空间因素的控制，苯甲酸的加入通过参与氢键的构建降低了活化能。理论化学研究表明，只有充分考虑手性催化剂的攻击方向，才能得到正确的计算结果。这项工作为利用吡啶环的 C2 位置和开发手性 2-取代 DMAP-N-氧化物作为有效的酰基转移催化剂铺平了道路。
• Composition containing a penem or carbapenem antibiotic
  申请人：SANKYO COMPANY LIMITED

  公开号：EP0226304B1

  公开（公告）日：1991-08-28
• Probing the Efficiency of N-Heterocyclic Carbene Promoted <i>O</i>- to C-Carboxyl Transfer of Oxazolyl Carbonates
  作者：Jennifer E. Thomson、Craig D. Campbell、Carmen Concellón、Nicolas Duguet、Kathryn Rix、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1021/jo702720a

  日期：2008.4.1

  Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.
• US4757066A
  申请人：——

  公开号：US4757066A

  公开（公告）日：1988-07-12
• Regiodivergent Enantioselective γ-Additions of Oxazolones to 2,3-Butadienoates Catalyzed by Phosphines: Synthesis of α,α-Disubstituted α-Amino Acids and <i>N</i>,<i>O</i>-Acetal Derivatives
  作者：Tianli Wang、Zhaoyuan Yu、Ding Long Hoon、Claire Yan Phee、Yu Lan、Yixin Lu

  DOI：10.1021/jacs.5b10524

  日期：2016.1.13

  Phosphine-catalyzed regiodivergent enantioselective C-2- and C-4-selective gamma-additions of oxazolones to 2,3-butadienoates have been developed. The C-4-selective gamma-addition of oxazolones occurred in a highly enantioselective manner when 2-aryl-4-alkyloxazol-5-(4H)-ones were employed as pronudeophiles. With the employment of 2-alkyl-4-aryloxazol-5-(4H)-ones as the donor, C-2-selective gamma-addition of oxazolones took place in a highly enantioselective manner. The C-4-selective adducts provided rapid access to optically enriched alpha,alpha-disubstituted alpha-amino acid derivatives, and the C-2-selective products led to facile synthesis of chiral N,O-acetals and gamma-lactols. Theoretical studies via DFT calculations suggested that the origin of the observed regioselectivity was due to the distortion energy that resulted from the interaction between the nudeophilic oxazolide and the electrophilic phosphonium intermediate.