(E)-ethyl 3-formyl-2-(4-methoxyphenylamino)undec-5-enoate

• 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: (E)-ethyl 3-formyl-2-(4-methoxyphenylamino)undec-5-enoate
• 英文别名: ethyl (E,2S,3R)-3-formyl-2-(4-methoxyanilino)undec-5-enoate
• 化学式: C₂₁H₃₁NO₄
• 分子量: 361.481
• InChiKey: LXVCDOKZWOQDNQ-KQLHMXSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  反-4-癸烯醛 、 Acetic acid, [(4-methoxyphenyl)imino]-, ethyl ester, (2E)- 在 (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid 作用下， 以 二甲基亚砜 为溶剂， 反应 3.0h， 以84%的产率得到(E)-ethyl 3-formyl-2-(4-methoxyphenylamino)undec-5-enoate
  参考文献：
  名称：

  Catalysis of 3-Pyrrolidinecarboxylic Acid and Related Pyrrolidine Derivatives in Enantioselective anti-Mannich-Type Reactions:  Importance of the 3-Acid Group on Pyrrolidine for Stereocontrol

  摘要：

  The development of enantioselective anti-selective Mannich-type reactions of aldehydes and ketones with imines catalyzed by 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives is reported in detail. Both (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid and (R)-3-pyrrolidinecarboxylic acid efficiently catalyzed the reactions of aldehydes with alpha-imino esters under mild conditions and afforded anti-Mannich products with high diastereo- and enantioselectivities (anti/syn up to 99:1, up to >99% ee). For the reactions of ketones with a-imino esters, (R)-3-pyrrolidinecarboxylic acid was an efficient catalyst (anti/syn up to >99:1, up to 99% ee). Evaluation of a series of pyrrolidine-based catalysts indicated that the acid group at the beta-position of the pyrrolidine ring of the catalyst played an important role in forwarding the carbon-carbon bond formation and in directing anti-selectivity and enantioselectivity.

  DOI：

  10.1021/ja074907+

文献信息

• anti-Selective SMP-catalyzed direct asymmetric Mannich-type reactions: synthesis of functionalized amino acid derivatives
  作者：Armando Córdova、Carlos F Barbas

  DOI：10.1016/s0040-4039(02)01772-0

  日期：2002.10

  The first (S)-2-methoxymethylpyrrolidine (SMP)-catalyzed direct asymmetric Mannich-type reactions of unmodified aldehydes with N-PMP-protected α-imino ethyl glyoxylate are described. The reaction proceeded in a highly anti-selective manner (dr up to 19:1) with enantioselectivities between 74 and 92%.

  描述了未改性的醛与N -PMP保护的α-亚氨基乙基乙醛酸酯的第一（S）-2-甲氧基甲基吡咯烷（SMP）催化的直接不对称曼尼希型反应。反应以高度反选择性的方式（dr高达19：1）进行，对映选择性在74％至92％之间。
• 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.
• Catalysis of 3-Pyrrolidinecarboxylic Acid and Related Pyrrolidine Derivatives in Enantioselective <i>anti</i>-Mannich-Type Reactions:  Importance of the 3-Acid Group on Pyrrolidine for Stereocontrol
  作者：Haile Zhang、Susumu Mitsumori、Naoto Utsumi、Masanori Imai、Noemi Garcia-Delgado、Maria Mifsud、Klaus Albertshofer、Paul Ha-Yeon Cheong、K. N. Houk、Fujie Tanaka、Carlos F. Barbas

  DOI：10.1021/ja074907+

  日期：2008.1.1

  The development of enantioselective anti-selective Mannich-type reactions of aldehydes and ketones with imines catalyzed by 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives is reported in detail. Both (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid and (R)-3-pyrrolidinecarboxylic acid efficiently catalyzed the reactions of aldehydes with alpha-imino esters under mild conditions and afforded anti-Mannich products with high diastereo- and enantioselectivities (anti/syn up to 99:1, up to >99% ee). For the reactions of ketones with a-imino esters, (R)-3-pyrrolidinecarboxylic acid was an efficient catalyst (anti/syn up to >99:1, up to 99% ee). Evaluation of a series of pyrrolidine-based catalysts indicated that the acid group at the beta-position of the pyrrolidine ring of the catalyst played an important role in forwarding the carbon-carbon bond formation and in directing anti-selectivity and enantioselectivity.