(+)-(S)-tert-butyl mandelate

• 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: (+)-(S)-tert-butyl mandelate
• 英文别名: (S)-tert-butyl 2-hydroxy-2-phenylacetate；tert-butyl (2S)-2-hydroxy-2-phenylacetate
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: HFQCAIQTDNARDZ-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 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)-tert-butyl mandelate 在 三乙烯二胺 作用下， 以 二甲基亚砜 为溶剂， 生成 苯乙酸,a-羟基-,1,1-二甲基乙基酯
  参考文献：
  名称：

  Controlled racemization and asymmetric transformation of α-substituted carboxylic acids in the melt

  摘要：

  The racemization and asymmetric transformation of a series of cx substituted carboxylic acids, viz. mandelic acid, hydratropic acid, ibuprofen and naproxen, were studied. Several racemization methods for mandelic acid were studied and it was found that base-catalyzed racemization in aprotic polar solvents was the most efficient method. Moreover, a fast and mild base-catalyzed racemization reaction in the melt was developed. DBN turned out to be a very efficient racemizing base for the substrates studied. Combination of the base-catalyzed racemization in the melt with known resolution processes resulted in crystallization-induced asymmetric transformations. Treating racemic ibuprofen or hydratropic acid with 1.5-2.5 equivalents of enantiopure alpha-methylbenzylamine and a catalytic amount of DBN resulted in the isolation of enantiomerically enriched ibuprofen or hydratropic acid with ees of up to 75% and almost quantitative yields. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00387-0
• 作为产物：
  描述：

  tert-butyl 2-(1H-imidazol-1-yl)-2-oxoacetate 在 copper(II) bis(trifluoromethanesulfonate) 、 2,6-Dimethyl-3,5-diisobutoxycarbonyl-1,4-dihydropyridine 、 (4S,4S')-(-)-2,2'-(1-methylethylidene)bis[4,5-dihydro-4-(phenylmethyl)oxazole] 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 48.0h， 生成 (+)-(S)-tert-butyl mandelate
  参考文献：
  名称：

  α-酮酸酯与汉驰酯的催化不对称转移加氢反应。

  摘要：

  C2对称的手性铜（II）-双恶唑啉类化合物可作为醇脱氢酶模拟物，并以Hantzsch酯作为合成的NADH类似物催化α-酮酸酯的高度对映选择性转移氢化，从而以极好的对映选择性提供α-羟基酯。[反应：请参见文字]。

  DOI：

  10.1021/ol0624373

文献信息

• A Highly Efficient and Enantioselective Intramolecular Cannizzaro Reaction under TOX/Cu(II) Catalysis
  作者：Pan Wang、Wen-Jie Tao、Xiu-Li Sun、Saihu Liao、Yong Tang

  DOI：10.1021/ja409859x

  日期：2013.11.13

  An asymmetric intramolecular Cannizzaro reaction of aryl and alkyl glyoxals with alcohols has been realized with an unprecedented high level of enantioselectivity, on the basis of a newly developed congested TOX ligand and a gradual liberation protocol of active glyoxals from glyoxal monohydrates. Preliminary results suggested a mechanism of enantioselective addition of alcohols to glyoxals contributing

  基于新开发的拥挤 TOX 配体和活性乙二醛从乙二醛一水合物中逐渐释放的方案，芳基和烷基乙二醛与醇的不对称分子内 Cannizzaro 反应以前所未有的高水平对映选择性实现。初步结果表明，除了半缩醛中间体的动态动力学拆分之外，醇对映选择性加成到乙二醛的机制对立体选择性贡献最大。
• METHODS AND COMPOSITIONS FOR PREVENTING OPIOID ABUSE
  申请人：Waterville Valley Technologies, Inc.

  公开号：US20160326182A1

  公开（公告）日：2016-11-10

  Abuse-resistant opioid compounds, drug delivery systems, pharmaceutical compositions comprising an opioid covalently bound to a chemical moiety are provided. Methods of delivering an active ingredient to a subject and methods of preventing opioid abuse are also provided.

  提供了耐滥用的阿片类化合物、药物输送系统、含有阿片类药物与化学基团共价结合的制药组合物。还提供了将活性成分输送给受试者的方法以及预防阿片类药物滥用的方法。
• Enantio- and chemoselective Brønsted-acid/Mg(ⁿBu)₂ catalysed reduction of α-keto esters with catecholborane
  作者：Dieter Enders、Bianca A. Stöckel、Andreas Rembiak

  DOI：10.1039/c4cc00427b

  日期：——

  The first enantio- and chemoselective Bronsted-acid catalysed reduction of alpha-keto esters with catecholborane has been developed. The alpha-hydroxy esters were obtained under mild reaction conditions in virtually quantitative yields and excellent enantioselectivities. With slight modifications both enantiomers can be obtained without any loss of selectivity.

  已开发出第一对映体和化学选择性布朗斯台德酸催化的儿茶酚硼烷还原α-酮酯。α-羟基酯是在温和的反应条件下以实际上定量的产率和优异的对映选择性而获得的。稍作修饰，即可得到两种对映体，而不会损失任何选择性。
• 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。
• Efficient Preparation of Aminoxyacyl Amides, Aminoxy Hybrid Peptides, and α-Aminoxy Peptides
  作者：Alan R. Katritzky、Ilker Avan、Srinivasa R. Tala

  DOI：10.1021/jo901612j

  日期：2009.11.20

  N-(Pg-α-aminoxy acids) 1a−g are converted to N-(Pg-α-aminoxyacyl)benzotriazoles 2a−g, which react under mild conditions with amines, α-amino acids/α-dipeptides, and α-aminoxy acids to give aminoxyacyl amides 3a−g, (3e+3e′), and (3g+3g′), aminoxy hybrid peptides 4a−h, (4a+4a′), 6a−d, 9a−e, (9a+9a′), and (9b+9b′), and α-aminoxy peptides 10a,b in good yields without racemization.

  将N-（Pg-α-氨氧基酸）1a - g转化为N-（Pg-α-氨氧基酰基）苯并三唑2a - g，使其在温和条件下与胺，α-氨基酸/α-二肽和α-氨氧基酸生成氨氧基酰基酰胺3a - g，（3e + 3e'）和（3g + 3g'），氨氧基杂合肽4a - h，（4a + 4a'），6a - d，9a - e，（9a + 9a'）和（9b + 9b'），以及α-氨氧基肽10a，b的产量高，没有消旋作用。