allyl (E)-2-((4-methoxyphenyl)imino)acetate | 203252-08-8

• 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: allyl (E)-2-((4-methoxyphenyl)imino)acetate
• CAS: 203252-08-8
• 化学式: C₁₂H₁₃NO₃
• 分子量: 219.24
• InChiKey: HCCNHWXYXHSICR-UKTHLTGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.13
• 重原子数：
  16.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  47.89
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  环己酮 、 allyl (E)-2-((4-methoxyphenyl)imino)acetate 在 (R)-吡咯烷-3-羧酸 作用下， 以 异丙醇 为溶剂， 反应 16.0h， 以95%的产率得到
  参考文献：
  名称：

  TRANS-3,5-DISUBSTITUTEDPYRROLIDINE: ORGANOCATALYST FOR anti-MANNICH REACTIONS

  摘要：

  披露了一种公式I的化合物，其中R是含有一个在距离与亚基连接的环碳三个原子以内的氢键形成原子的取代基；X是CH2，O，S或NR1，其中R1是一个含有一个到约18个碳原子的烃基团或一个氨基保护基团；R2是氢化物或含有一个到约十二个碳原子的烃基团；R3是氢化物或甲基，但是当X是CH2时，R2和R3不能都是氢化物。公式I的分子以及其中R2和R3都可以是氢化物（公式X）的分子，在曼尼希反应中作为催化剂，非对称地形成具有相邻碳原子上的两个手性中心的β-氨基醛或β-氨基酮对映异构体产品，并且反式对映异构体过剩于顺式对映异构体。还披露了进行那些合成的方法。

  公开号：

  US20070117986A1
• 作为产物：
  描述：

  allyl (4-methoxyphenyl)glycinate 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以87%的产率得到allyl (E)-2-((4-methoxyphenyl)imino)acetate
  参考文献：
  名称：

  制备α-氨基羧酸衍生物的简便方法及其在非天然α-氨基酸衍生物的不对称合成中的应用。

  摘要：

  我们在本文中描述了锰（IV）介导的Np-甲氧基苯基（PMP）保护的甘氨酸衍生物的氧化，用于合成α-亚氨基羧酸衍生物。使用这种方法，避免了不稳定的乙二酸衍生物的利用。此外，使用这种方法，我们合成了新型的α-亚氨基羧酸衍生物，例如α-亚氨基苯基酯，全氟烷基酯，酰亚胺和硫代酯。还描述了这些新型亚胺衍生物与1,3-二羰基化合物的不对称曼尼希反应，与使用常规α-亚氨基酯型底物相比，新型α-亚氨基酰亚胺具有更高的化学收率和立体选择性。 。

  DOI：

  10.1248/cpb.c17-00158

文献信息

• <i>anti</i>-Selective Direct Asymmetric Mannich Reactions Catalyzed by Axially Chiral Amino Sulfonamide as an Organocatalyst
  作者：Taichi Kano、Yukako Yamaguchi、Osamu Tokuda、Keiji Maruoka

  DOI：10.1021/ja056008w

  日期：2005.11.30

  A direct asymmetric Mannich reaction using a novel axially chiral amino trifluoromethanesulfonamide (S)-3 has been developed in highly anti-selective and enantioselective manners. Thus, in the presence of a catalytic amount of (S)-3, the reactions between aldehydes and the alpha-imino ester 4 proceed smoothly to give the functional beta-amino aldehydes with significantly higher anti/syn ratio and enantioselectivity

  已经以高度抗选择性和对映选择性方式开发了使用新型轴向手性氨基三氟甲磺酰胺 (S)-3 的直接不对称曼尼希反应。因此，在催化量的 (S)-3 存在下，醛和 α-亚氨基酯 4 之间的反应顺利进行，得到具有比以前可能更高的反/顺比和对映选择性的功能性 β-氨基醛。
• 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.
• 3-Pyrrolidinecarboxylic Acid for Direct Catalytic Asymmetric <i>a</i><i>nti</i>-Mannich-Type Reactions of Unmodified Ketones
  作者：Haile Zhang、Maria Mifsud、Fujie Tanaka、Carlos F. Barbas

  DOI：10.1021/ja062950b

  日期：2006.8.1

  We report the development of direct catalytic, enantioselective, anti-selective Mannich-type reactions between unmodified ketones and alpha-imino esters under mild conditions. The reactions were performed using 5-10 mol % of (R)-3-pyrrolidinecarboxylic or (R)-beta-proline as catalyst in an environmentally benign solvent, 2-PrOH, at room temperature. The anti-Mannich products were obtained in good yields with high diastereo- and enantioselectivities (up to anti/syn >99:1, 99% ee). While (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid is an excellent catalyst for the anti-Mannich-type reactions of aldehydes, it did not efficiently catalyze the corresponding Mannich-type reactions of ketones; (R)-3-pyrrolidinecarboxylic acid did efficiently catalyze the Mannich-type reactions of ketones. (S)-Proline or (S)-2-pyrrolidinecarboxylic acid has been reported to catalyze the Mannich-type reactions of ketones to afford the syn-products. Thus, the position of the carboxylic acid group on the pyrrolidine ring directs the stereoselection of the catalyzed reaction, providing either syn- or anti-Mannich products.
• A new multicomponent synthesis of 1,2,3,4-tetrahydroquinolines
  作者：Rita Annunziata、Mauro Cinquini、Franco Cozzi、Valentina Molteni、Olaf Schupp

  DOI：10.1016/s0040-4020(97)00594-2

  日期：1997.7

  The synthesis of a variety of differently substituted 1,2,3,4-tetrahydroquinolines by a new three-component reaction involving an imine (Ar-N=CHR), an a-branched and enolizable aldehyde ((RRCHCHO)-R-1-C-2), and a nucleophile (ROH, ArSH, ArNH2, H2O) is described. The in situ generation of the imine (that allows a four-component process), and the reactions of an enantiomerically pure imine and/or aldehyde were also studied. A short discussion of the reaction mechanism is reported. (C) 1997 Elsevier Science Ltd.
• A Convenient Method for Preparation of α-Imino Carboxylic Acid Derivatives and Application to the Asymmetric Synthesis of Unnatural α-Amino Acid Derivative
  作者：Tsubasa Inokuma、Takahisa Jichu、Kodai Nishida、Akira Shigenaga、Akira Otaka

  DOI：10.1248/cpb.c17-00158

  日期：——

  glycine derivatives for the synthesis of α-imino carboxylic acid derivatives. Using this methodology, utilization of unstable glyoxic acid derivatives was avoided. Furthermore, using this methodology we synthesized novel α-imino carboxylic acid derivatives such as α-imino phenyl ester, perfluoroalkyl etsers, imides, and thioester. The asymmetric Mannich reaction of those novel imine derivatives with 1

  我们在本文中描述了锰（IV）介导的Np-甲氧基苯基（PMP）保护的甘氨酸衍生物的氧化，用于合成α-亚氨基羧酸衍生物。使用这种方法，避免了不稳定的乙二酸衍生物的利用。此外，使用这种方法，我们合成了新型的α-亚氨基羧酸衍生物，例如α-亚氨基苯基酯，全氟烷基酯，酰亚胺和硫代酯。还描述了这些新型亚胺衍生物与1,3-二羰基化合物的不对称曼尼希反应，与使用常规α-亚氨基酯型底物相比，新型α-亚氨基酰亚胺具有更高的化学收率和立体选择性。 。