(S)-1-naphtylglycolic acid methyl ester | 167820-08-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-1-naphtylglycolic acid methyl ester
• 英文别名: (S)-methyl 1-naphthylglycolate；(+)-methyl (S)-α-hydroxy-α-(1-naphthyl)acetate；methyl 2-hydroxy-2-(naphthalen-1-yl)acetate；(S)-hydroxy-(naphthyl-(1))-acetic acid methyl ester；(S)-Hydroxy-(naphthyl-(1))-essigsaeure-methylester；methyl (2S)-2-hydroxy-2-naphthalen-1-ylacetate
• CAS: 167820-08-8
• 化学式: C₁₃H₁₂O₃
• 分子量: 216.236
• InChiKey: MLGAFFCIJKBSBD-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-1-naphtylglycolic acid methyl ester 、 乙酸酐 在 吡啶 作用下， 反应 6.0h， 以83%的产率得到(S)-α-acetoxy-α-(1-naphtyl)acetate
  参考文献：
  名称：

  Brønsted Acid Catalysis of Achiral Enamine for Regio- and Enantioselective Nitroso Aldol Synthesis

  摘要：

  Two types of chiral Brønsted acid catalysts have been shown to catalyze regio- and enantioselective nitroso aldol synthesis between nitrosobenzene and achiral enamine. The combination of Brønsted acidity and amine moiety of enamine realizes complete regioselectivity with high enantioselectivity. After a survey of Brønsted acid catalysts, 1-naphthyl glycolic acid is found to be optimal in the O-nitroso aldol pathway, while 1-naphthyl TADDOL is the best catalyst for the N-nitroso aldol pathway. This is based on our finding on the control of regioselectivity by changing the amine moiety of enamine and the choice of Brønsted acidity.

  DOI：

  10.1021/ja0444637
• 作为产物：
  描述：

  1-萘甲醛 、 alkaline earth salt of/the/ methylsulfuric acid 在 氢氧化钾 、 氯化铪(IV)四氢呋喃络合物 、 lithium chloride 作用下， 以 1,4-二氧六环 为溶剂， 反应 30.0h， 生成 (S)-1-naphtylglycolic acid methyl ester
  参考文献：
  名称：

  Brønsted Acid Catalysis of Achiral Enamine for Regio- and Enantioselective Nitroso Aldol Synthesis

  摘要：

  Two types of chiral Brønsted acid catalysts have been shown to catalyze regio- and enantioselective nitroso aldol synthesis between nitrosobenzene and achiral enamine. The combination of Brønsted acidity and amine moiety of enamine realizes complete regioselectivity with high enantioselectivity. After a survey of Brønsted acid catalysts, 1-naphthyl glycolic acid is found to be optimal in the O-nitroso aldol pathway, while 1-naphthyl TADDOL is the best catalyst for the N-nitroso aldol pathway. This is based on our finding on the control of regioselectivity by changing the amine moiety of enamine and the choice of Brønsted acidity.

  DOI：

  10.1021/ja0444637

文献信息

• Synthesis of chiral α-aryl-α-hydroxyacetic acids: Substituent effects in pig liver acetone powder (PLAP) induced enantioselective hydrolysis
  作者：Deevi Basavaiah、Peddinti Rama Krishna

  DOI：10.1016/0040-4020(94)01105-9

  日期：1995.2

  Pig liver acetone powder (PLAP) catalyzed hydrolysis of alkyl α-acetoxy-α-arylacetates produces alkyl (S)-α-aryl-α-hydroxyacetates in 23–80% enantiomeric purities. Enantioselectivity is dependent on the ester group of O-acetylmandelates. Substitution on the aromatic ring results in inferior selectivities. Only acetate group is hydrolyzed by PLAP while the ester functionality is found to be completely

  猪肝脏丙酮粉（PLAP）烷基α乙酰氧基α-arylacetates的催化的水解产生烷基（小号） - α -芳基- α -hydroxyacetates在23-80％对映体纯度。对映选择性取决于O-乙酰扁桃酸酯的酯基。芳环上的取代导致较差的选择性。PLAP仅水解乙酸酯基团，而发现酯官能团是完全完整的。
• Chemoenzymatic Preparation of Enantiomerically Enriched (<i>R</i>)‐(–)‐Mandelic Acid Derivatives: Application in the Synthesis of the Active Agent Pemoline
  作者：Marcin Poterała、Maciej Dranka、Paweł Borowiecki

  DOI：10.1002/ejoc.201700161

  日期：2017.4.26

  resolution of several racemic derivatives of mandelic acid methyl ester catalyzed by lipases from Pseudomonas fluorescens (Amano AK) or Burkholderia cepacia (Amano PS-C II and Amano PS-IM) has been achieved. A gram-scale lipase-mediated kinetic resolution approach has been developed that allows the facile synthesis of the corresponding methyl (R)-(–)-mandelates with excellent enantiomeric excesses (up to

  已经实现了由荧光假单胞菌 (Amano AK) 或洋葱伯克霍尔德菌 (Amano PS-C II 和 Amano PS-IM) 的脂肪酶催化的扁桃酸甲酯的几种外消旋衍生物的对映选择性拆分。已经开发出一种克级脂肪酶介导的动力学拆分方法，可以轻松合成相应的甲基 (R)-(–)-扁桃酸，具有出色的对映体过量（高达 > 99 % ee）和反应对映选择性（E 值高达到 >200）。用于治疗注意力缺陷多动障碍 (ADHD) 和发作性睡病的多巴胺能药物 pemoline 是通过在碱性条件下将制备的 (R)-(-)-扁桃酸甲酯与盐酸胍缩合，以 98% 的 ee 直接合成的。使适应。光学纯形式的所需 (R)-(+)-pemoline (> 从乙醇中重结晶两次后获得 99% ee)。然而，手性 HPLC 证实旋光性匹莫林在甲醇溶液中发生外消旋化。
• Organocatalytic conversion of arylglyoxals into optically active mandelic acid derivatives
  作者：Ellen Schmitt、Ingo Schiffers、Carsten Bolm

  DOI：10.1016/j.tetlet.2009.01.114

  日期：2009.7

  A novel protocol for the organocatalytic conversion of arylglyoxals into the corresponding α-hydroxy arylacetic acid methyl esters has been developed. The catalyst consists of a combination of a commercially available cinchona alkaloid derivative and an achiral thiol and leads to enantiomerically enriched products (eemax 83%) under mild reaction conditions. The alkaloid can be easily recovered and

  已经开发出一种新的方案，用于将芳基乙二醛有机催化转化为相应的α-羟基芳基乙酸甲酯。该催化剂由市售的金鸡纳生物碱衍生物和非手性硫醇组成，在温和的反应条件下可生成对映体富集的产物（ee最高为83％）。生物碱可以容易地回收和再利用而不会损失活性和选择性。
• Enantioselective homoallyl-cyclopropanation of dibenzylideneacetone by modified allylindium halide reagents—rapid access to enantioenriched 1-styryl-norcarene
  作者：Guy C. Lloyd-Jones、Philip D. Wall、Jennifer L. Slaughter、Alexandra J. Parker、David P. Laffan

  DOI：10.1016/j.tet.2006.05.003

  日期：2006.12

  ligands have been tested as stoichiometric asymmetric modifiers for this process. Enantiopure compounds such as cinchona alkaloids, ephedra, aminoalcohols and tartaric acid derivatives, which have proven of utility as asymmetric modifiers for the indium-mediated allylation of aldehydes and ketones, were very inefficient in the process 8→9. However, mandelic acid derivatives, in particular mandelates, were

  二亚苄基丙酮（8）与原位生成的烯丙基卤化试剂反应生成均烯丙基环丙烷化反应的产物：2-（3''-丁烯基）-1,1-双[（E）-2'-苯基乙烯基]环丙烷（9），其通过逐步分离CO键和从试剂中递送两个烯丙基片段来进行。已经测试了一系列对映体富集的配体作为该过程的化学计量不对称改性剂。对映纯化合物，例如金鸡纳生物碱，麻黄，氨基醇和酒石酸衍生物，已被证明可用作铟介导的醛和酮的烯丙基化的不对称改性剂，但在此过程中效率很低8 → 9。然而，发现扁桃酸衍生物，特别是扁桃酸酯具有很大的潜力。环丙烷9的绝对立体化学已通过降解为1,1-二羧甲基-2-丁基环丙烷，并从己烯开始进行独立的对映选择性合成来确定。在优化的条件下，即。使用烯丙基碘化试剂并与Na 2 SO 3水溶液进行后处理以避免碘介导的聚合，可以以86％的收率生成（S）-9，并使用（S）扁桃酸甲酯作为改性剂有用的对映体纯度（94/6 er ） 被观测到。
• Dual Pathway for the Asymmetric Transfer Hydrogenation of α-Ketoimides to Chiral α-Hydroxy Imides or Chiral α-Hydroxy Esters
  作者：Qiankun Zhao、Yuxi Zhao、Hang Liao、Tanyu Cheng、Guohua Liu

  DOI：10.1002/cctc.201500906

  日期：2016.1

  two types of chiral products through a controllable strategy in asymmetric catalysis. Herein, we develop Ru‐catalysed asymmetric transfer hydrogenation of α‐ketoimides to realise an enantioselective construction of chiral α‐hydroxy imides or chiral α‐hydroxy esters. The transformation of α‐ketoimides catalysed by (S,S)‐[RuCl(η6‐mesitylene)diamine] can afford various chiral α‐hydroxy imides with high yields

  在对映选择性反应中，我们希望通过不对称催化中的可控策略获得两种类型的手性产物。本文中，我们开发了Ru催化的α-酮酰亚胺的不对称转移加氢反应，以实现手性α-羟基酰亚胺或手性α-羟基酯的对映选择性结构。α-ketoimides的由（催化的转化小号，小号） -将[RuCl（η 6 -mesitylene）二胺]可以承受高的产率和对映选择性的手性的各种α羟基酰亚胺，而由（催化的小号，小号） -将[RuCl （η 6[-六甲基苯）二胺]通过稍微调节反应条件得到所需的手性α-羟基酯。此处描述的方法是在温和的反应条件下以甲酸钠为氢源进行可控的有机转化，这种转化的好处是可以从α-酮酰亚胺中选择性地获得各种手性α-羟基酰亚胺或α-羟基酯。