(2S,3S)-ethyl 3-formyl-2-[(4-methoxyphenyl)amino]hexanoate | 873692-29-6

• 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: (2S,3S)-ethyl 3-formyl-2-[(4-methoxyphenyl)amino]hexanoate
• 英文别名: (2S,3S)-ethyl 3-formyl-2-(4-methoxyphenylamino)hexanoate；ethyl (2S,3S)-3-formyl-2-(p-methoxyphenylamino)hexanoate；ethyl (2S,3S)-3-formyl-2-(4-methoxyanilino)hexanoate
• CAS: 873692-29-6
• 化学式: C₁₆H₂₃NO₄
• 分子量: 293.363
• InChiKey: XDKVFHZADLTAJZ-DOMZBBRYSA-N

物化性质

• 沸点：
  435.1±45.0 °C(Predicted)
• 密度：
  1.100±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  二乙基氰化铝 、 (2S,3S)-ethyl 3-formyl-2-[(4-methoxyphenyl)amino]hexanoate 以 乙醚 、 甲苯 为溶剂， 反应 3.0h， 生成 etyl (2S,3S)-3-[(R)-cyanohydroxymethyl]-2-(p-methoxyphenylamino)-hexanoate
  参考文献：
  名称：

  一锅不对称合成β-氰基羟甲基α-氨基酸衍生物：形成三个连续的立体中心。

  摘要：

  [反应：见正文]描述了一锅不对称曼尼希氢氰化反应。在催化量的L-脯氨酸存在下，未修饰的醛与N-PMP保护的α-亚氨基乙基乙醛酸酯的反应，然后添加Et（2）AlCN，提供高度对映体纯的β-氰基羟甲基α-氨基酸衍生物，具有三个连续立体异构中心为单一非对映异构体（93-99％ee）。在氰化步骤中控制反应温度指导产物是否发生环化成内酯。

  DOI：

  10.1021/ol027048x
• 作为产物：
  描述：

  正戊醛 、 ethyl (4-methoxyphenylimino)acetate 在 N-[3,5-双(三氟甲基)苯基]-N′-[(9R)-6′-甲氧基-9-金鸡宁]硫脲 、 L-脯氨酸 作用下， 以 neat (no solvent) 为溶剂， 反应 0.25h， 以93%的产率得到(2S,3S)-ethyl 3-formyl-2-[(4-methoxyphenyl)amino]hexanoate
  参考文献：
  名称：

  List–Barbas–Mannich Reaction Catalyzed by Modularly Designed Organocatalysts

  摘要：

  The List-Barbas-Mannich reaction of ethyl (p-methoxyphenylimino)acetate (p-methoxyphenyl = PMP) with unmodified aldehydes or ketones catalyzed by modularly designed organocatalysts (MDOs) that are self-assembled from proline and cinchona alkaloid thioureas (such as a quinidine-derived thiourea) produces the corresponding gamma-oxo-alpha-amino acid derivatives in high yields and excellent stereoselectivities. No solvent is necessary for this reaction. Aldehydes are especially good substrates for this reaction: The reaction takes only a few minutes to yield the corresponding List-Barbas-Mannich products in excellent dr (up to >99:1) and ee values (up to >99% ee).

  DOI：

  10.1021/jo4019304

文献信息

• Organic Solvent-Free, Enantio- and Diastereoselective, Direct Mannich Reaction in the Presence of Water
  作者：Yujiro Hayashi、Tatsuya Urushima、Seiji Aratake、Tsubasa Okano、Kazuki Obi

  DOI：10.1021/ol702489k

  日期：2008.1.1

  An organocatalyst-mediated, asymmetric Mannich reaction in the presence of water without using organic solvents has been developed. A highly reactive siloxytetrazole hybrid catalyst has been developed for the reaction of dimethoxyacetaldehyde, while the sodium salt of siloxyproline is an effective catalyst of alpha-imino glyoxylate. Excellent enantioselectivity can be realized, and the usage of organic

  已经开发了在不使用有机溶剂的情况下在水存在下的有机催化剂介导的不对称曼尼希反应。已经开发出高反应性的甲硅烷氧基四唑杂化催化剂用于二甲氧基乙醛的反应，而甲硅烷氧基脯氨酸的钠盐是α-亚氨基乙醛酸酯的有效催化剂。与在有机溶剂中的常规反应相比，可以实现优异的对映选择性，并且可以减少有机溶剂的使用。
• 4-Aminothiourea Prolinol<i>tert</i>-Butyldiphenylsilyl Ether: A Chiral Secondary Amine-Thiourea as Organocatalyst for Enantioselective<i>anti</i>-Mannich Reactions
  作者：Hui Zhang、Yongming Chuan、Zhengyu Li、Yungui Peng

  DOI：10.1002/adsc.200900399

  日期：2009.10

  anti-Selective Mannich reactions of N-p-methoxyphenyl (PMP)-protected α-iminoglyoxylate with unmodified aldehydes or ketones were effectively catalyzed by 4-aminothiourea prolinol tert-butyldiphenylsilyl ether. The reactions led to chiral β-amino carbonyl compounds in high yields (up to 94%), excellent diastereo- and enantioselectivities (up to 98% de and >99% ee). The study demonstrated for the first

  抗的-选择性曼尼希反应ñ - p -甲氧基苯基（PMP）与未改性的醛或酮-保护的α-iminoglyoxylate得到有效利用4-氨基硫脲脯氨醇催化叔-butyldiphenylsilyl醚。反应导致高收率（高达94％），出色的非对映异构和对映选择性（高达98％de和> 99％ee）的手性β-氨基羰基化合物。该研究首次证明，仲胺-硫脲手性有机催化剂可促进未修饰醛或酮与α-亚氨基乙醛酸酯的直接曼尼希型反应。
• Enantioselective Organocatalytic Mannich Reactions with Autocatalysts and Their Mimics
  作者：Xinbo Wang、Yongbo Zhang、Haibo Tan、Yanchao Wang、Peng Han、David Zhigang Wang

  DOI：10.1021/jo902500b

  日期：2010.4.2

  The Mannich reactions previously extensively investigated with organocatalysis of L-proline and other related small molecules were reinvestigated with detailed stercochemical analysis of their autocatalysis pathways, through employment of both the products themselves and their close structural mimics as the catalysts. These organo-autocatalytic processes function as meaningful molecular models toward understanding the origin and maintenance of homochirality under biologically relevant conditions.