methyl R-(-)-atrolactate

• 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: methyl R-(-)-atrolactate
• 英文别名: (R)-(-)-methyl atrolactate；methyl (2R)-2-hydroxy-2-phenylpropanoate
• 化学式: C₁₀H₁₂O₃
• 分子量: 180.203
• InChiKey: CDMFKOGXDUTORS-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  methyl R-(-)-atrolactate 在 palladium 10% on activated carbon 、 二(对硝基苯基)叠氮膦酸酯 、 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 16.5h， 生成 H-(αMe)Phg-OMe
  参考文献：
  名称：

  季碳中心的S N 2置换：α，α-二取代的α-氨基酸合成的新途径

  摘要：

  已开发出一种使用双（对硝基苯基）磷叠氮酸酯在季碳原子上进行S N 2反应的新方法。手性叔醇被完全转化为构型，直接转化为相应的手性叔叠氮化物。通过催化氢化将叠氮化物转化为相应的胺，可以制备几种α，α-二取代的α-氨基酯或氨基酸。

  DOI：

  10.1016/j.tetlet.2015.01.041
• 作为产物：
  描述：

  DL-阿卓乳酸半水物 在 盐酸 作用下， 以 甲醇 、 正己烷 、 水 、 甲苯 为溶剂， 反应 3.0h， 生成 methyl R-(-)-atrolactate
  参考文献：
  名称：

  Solvent-induced chirality switching in the enantioseparation of regioisomeric hydroxyphenylpropionic acids via diastereomeric salt formation with (1 R ,2 S )-2-amino-1,2-diphenylethanol

  摘要：

  The enantioseparation of three hydroxyphenylpropionic acid isomers via diastereomeric salt formation with (1R,2S)-2-amino-1,2-diphenylethanol has been demonstrated. The racemates of all three acid isomers were successfully separated with high efficiency (0.56-0.84) after single crystallization. For 2-hydroxy-3-phenylpropionic acid 4, the configuration of the less-soluble salt was controlled by the crystallization solvent: the (R)-4 salt was crystallized from water, while 2-propanol afforded the (S)-4 salt. The chiral recognition mechanism of the three acids was discussed based on the crystal structures of the diastereomeric salts. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.02.011

文献信息

• Enantioselective addition of organozinc reagents to carbonyl compounds catalyzed by a camphor derived chiral γ-amino thiol ligand
  作者：Hsyueh-Liang Wu、Ping-Yu Wu、Ying-Ni Cheng、Biing-Jiun Uang

  DOI：10.1016/j.tet.2015.07.038

  日期：2016.5

  synthesis of the chiral camphor derived γ-amino thiol ligand 17 and its application in catalytic enantioselective carbon-carbon forming reactions through the addition of organozinc reagents to carbonyl compounds is described. The catalytic activity and enantioselectivity of ligand 17 is demonstrated in the enantioselective addition of various organozinc reagents to aldehydes and ketoesters, offering the corresponding

  在本文中，描述了手性樟脑衍生的γ-氨基硫醇配体17的设计和合成，以及通过向羰基化合物中添加有机锌试剂在催化对映选择性碳-碳形成反应中的应用。配体17的催化活性和对映选择性通过将各种有机锌试剂对映选择性加成到醛和酮酯中得到证明，从而以高收率和对映选择性提供相应的醇。还讨论了巯基在有机锌与醛的高度对映选择性1,2加成反应中的作用。
• A NEW AND EFFECTIVE ASYMMETRIC SYNTHESIS OF 3-PHENYLALKANALS
  作者：Teruaki Mukaiyama、Hiroki Hayashi、Tetsuo Miwa、Koichi Narasaka

  DOI：10.1246/cl.1982.1637

  日期：1982.10.5

  Highly optically active 3-phenylalkanals were obtained by the reaction of alkyl halides and a chiral homoenolate equivalent derived from the cinnamyl ether 3 and potassium diisopropylamide, followed by acidic hydrolysis.

  通过卤代烷与从肉桂醚3和二异丙胺钾衍生的手性同烯酸盐等效物的反应，得到高光学活性的3-苯基烷醛，随后进行酸水解。
• Isothiourea‐Catalyzed Acylative Kinetic Resolution of Tertiary α‐Hydroxy Esters
  作者：Shen Qu、Samuel M. Smith、Víctor Laina‐Martín、Rifahath M. Neyyappadath、Mark D. Greenhalgh、Andrew D. Smith

  DOI：10.1002/anie.202004354

  日期：2020.9.14

  acylative kinetic resolution (KR) of acyclic tertiary alcohols has been developed. Selectivity factors of up to 200 were achieved for the KR of tertiary alcohols bearing an adjacent ester substituent, with both reaction conversion and enantioselectivity found to be sensitive to the steric and electronic environment at the stereogenic tertiary carbinol centre. For more sterically congested alcohols

  已开发出高度对映选择性的异硫脲催化的无环叔醇的酰基动力学拆分（KR）。对于带有相邻酯取代基的叔醇的KR，选择性因子高达200，反应转化率和对映体选择性均对立体异构叔丁醇中心的空间和电子环境敏感。对于空间上更拥挤的醇，最合适的方法是使用最新开发的异硒脲催化剂，对映选择性相当，但与异硫脲HyperBTM相比，转化率更高。非对映体酰化过渡态模型被提出以合理化此过程中对映歧化的起源。
• Enantioselective Addition of Dimethylzinc to α-Keto Esters
  作者：José Pedro、Gonzalo Blay、Isabel Fernández、Alícia Marco-Aleixandre

  DOI：10.1055/s-2007-983851

  日期：2007.12

  The readily available (+)-N-Benzyl-(S)-mandelamide catalyzes the enantioselective addition of dimethylzinc to α-keto esters to give α-methyl-α-hydroxy esters containing stereogenic quaternary centers with moderate to good yields (56-87%). A good enantioselectivity of the reaction is obtained for aryl and heteroaryl keto esters. For these substrates ee values of 75-90% are obtained. The enantioselectivity

  容易获得的 (+)-N-苄基-(S)-扁桃酰胺催化二甲基锌与 α-酮酯的对映选择性加成，得到含有立体季铵中心的 α-甲基-α-羟基酯，产率适中至高 (56-87 %）。对于芳基和杂芳基酮酯，反应具有良好的对映选择性。对于这些基材，获得了 75-90% 的 ee 值。对于带有脂肪链的底物，对映选择性稍低。
• Enantioselective synthesis of quaternary stereogenic centers through catalytic asymmetric addition of dimethylzinc to α-ketoesters with chiral cis-cyclopropane-based amide alcohol as ligand
  作者：Bing Zheng、Shicong Hou、Zhiyuan Li、Hongchao Guo、Jiangchun Zhong、Min Wang

  DOI：10.1016/j.tetasy.2009.07.050

  日期：2009.9

  A new amino alcohol with a chiral cyclopropane backbone has been developed and used in the catalytic asymmetric diethylzinc addition to various types of α-ketoesters. This cyclopropane-based chiral amino alcohol shows moderate enantioselectivity in the addition of organozinc to α-ketoesters. For dimethylzinc addition to α-ketoesters, up to 81% ee are obtained, respectively.

  已开发出具有手性环丙烷骨架的新型氨基醇，并将其用于催化不对称二乙基锌除各种类型的α-酮酸酯中。这种基于环丙烷的手性氨基醇在将有机锌添加到α-酮酸酯中时显示出中等的对映选择性。对于将二甲基锌添加到α-酮酸酯中，分别获得了高达81％的ee。