ethyl 2-(p-methoxyphenylamino)-2-(2’-oxocycloheptyl)acetate

• 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: ethyl 2-(p-methoxyphenylamino)-2-(2’-oxocycloheptyl)acetate
• 英文别名: ethyl 2-(4-methoxyphenylamino)-2-(2'-oxocycloheptyl)acetate；ethyl 2-(p-methoxyphenylamino)-2-(2'-oxocycloheptyl)acetate；Ethyl 2-(4-methoxyanilino)-2-(2-oxocycloheptyl)acetate；ethyl 2-(4-methoxyanilino)-2-(2-oxocycloheptyl)acetate
• 化学式: C₁₈H₂₅NO₄
• 分子量: 319.401
• InChiKey: XGAOLBNNFSTSFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  2-(4-甲氧基苯基氨基)乙酸乙酯 、 环庚酮 在 tris(bipyridine)ruthenium(II) dichloride hexahydrate 、 copper(II) acetate monohydrate 、 (R)-N-(pyrrolidin-3-yl)trifluoromethanesulfonamide 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以97%的产率得到
  参考文献：
  名称：

  甘氨酸衍生物与酮和醛的对映选择性好氧氧化交叉脱氢反应通过协同光氧化还原催化和有机催化

  摘要：

  光氧化还原催化和烯胺催化的结合使甘氨酸衍生物与简单的酮或醛之间的对映选择性好氧氧化交叉脱氢偶联成为可能，这为快速合成对映纯的非天然α-烷基α-氨基酸衍生物提供了一种有效的方法。高收率，非对映异构体（高达> 99：1）和对映选择性（高达97％ee）。此过程包括将甘氨酸衍生物直接光诱导氧化为亚胺中间体，然后与原位生成的烯胺中间体进行不对称曼尼希型反应由酮或醛和手性仲胺有机催化剂制得。这种温和的方法可以直接形成C–C键，同时安装两个新的立体中心，而不会浪费掉官能团。

  DOI：

  10.1039/d0sc00683a

文献信息

• Asymmetric anti-Mannich reactions in continuous flow
  作者：Rafael Martín-Rapún、Sonia Sayalero、Miquel A. Pericàs

  DOI：10.1039/c3gc41444b

  日期：——

  A polystyrene-supported, pyrrolidine-based catalyst depicting very high activity and excellent stereoselectivity in the anti-Mannich reaction of aldehydes and ketones has been developed. The very robust, immobilized catalyst has been successfully used in the implementation of a continuous flow process with short residence times (down to 6 min) for the production of highly enantioenriched anti-type Mannich adducts at the preparative scale.

  开发了一种在醛和酮的反曼尼希反应中表现出极高活性和优异立体选择性的聚苯乙烯负载吡咯烷基催化剂。这种非常坚固的固定化催化剂已成功应用于连续流动工艺的实施，该工艺具有短停留时间（低至6分钟），用于制备规模上生产高度对映体富集的反式曼尼希加合物。
• Enantioselective aerobic oxidative cross-dehydrogenative coupling of glycine derivatives with ketones and aldehydes <i>via</i> cooperative photoredox catalysis and organocatalysis
  作者：Xiaorong Yang、Zhixiang Xie、Ying Li、Yuan Zhang

  DOI：10.1039/d0sc00683a

  日期：——

  glycine derivatives and simple ketones or aldehydes, which provides an efficient approach for the rapid synthesis of enantiopure unnatural α-alkyl α-amino acid derivatives in good yield with excellent diastereo- (up to >99 : 1) and enantioselectivities (up to 97% ee). This process includes the direct photoinduced oxidation of glycine derivatives to an imine intermediate, followed by the asymmetric Mannich-type

  光氧化还原催化和烯胺催化的结合使甘氨酸衍生物与简单的酮或醛之间的对映选择性好氧氧化交叉脱氢偶联成为可能，这为快速合成对映纯的非天然α-烷基α-氨基酸衍生物提供了一种有效的方法。高收率，非对映异构体（高达> 99：1）和对映选择性（高达97％ee）。此过程包括将甘氨酸衍生物直接光诱导氧化为亚胺中间体，然后与原位生成的烯胺中间体进行不对称曼尼希型反应由酮或醛和手性仲胺有机催化剂制得。这种温和的方法可以直接形成C–C键，同时安装两个新的立体中心，而不会浪费掉官能团。
• Enantioselective anti-Mannich reaction catalyzed by modularly designed organocatalysts
  作者：Swapna Konda、John C.-G. Zhao

  DOI：10.1016/j.tet.2018.09.006

  日期：2018.10

  te was realized using the modularly designed organocatalysts (MDOs) self-assembled from cinchona alkaloid derivatives and (R)-pyrrolidien-3-carboxylic acid in the reaction media. The desired anti-Mannich products were obtained in good to excellent yields (up to 93%), excellent diastereoselectivities (up to 99:1 dr), and good to high enantioselectivities (up to 99% ee).

  利用金鸡纳生物碱衍生物和( R )-吡咯烷-3-羧基自组装的模块化设计的有机催化剂(MDO)，实现了醛和酮与(4-甲氧基苯基亚氨基)乙酸乙酯的反曼尼希反应的高度立体选择性方法反应介质中的酸。所需的抗曼尼希产物以良好到优异的产率（高达 93%）、优异的非对映选择性（高达 99:1 dr）和良好到高的对映选择性（高达 99% ee）获得。
• 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.