(S)-3-(tert-butoxycarbonyl)-4-benzyl-2-oxazolidinone | 132836-68-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (S)-3-(tert-butoxycarbonyl)-4-benzyl-2-oxazolidinone
• 英文别名: tert-butyl (4S)-4-benzyl-2-oxo-1,3-oxazolidine-3-carboxylate
• CAS: 132836-68-1
• 化学式: C₁₅H₁₉NO₄
• 分子量: 277.32
• InChiKey: JGAMPTLBAFMYOO-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-3-(tert-butoxycarbonyl)-4-benzyl-2-oxazolidinone 在 甲醇 、 1-[2-[methoxy-[2-(methylaminomethyl)phenyl]boranyl]phenyl]-N-methylmethanamine 作用下， 25.0 ℃ 、101.33 kPa 条件下， 反应 13.0h， 以90%的产率得到N-Boc-L-苯丙氨醇
  参考文献：
  名称：

  氨基有机硼配合物的双重分子识别：β-二羰基衍生物的选择性醇解

  摘要：

  双重职责：氨基有机硼酸盐（AOB）络合物识别醇和β-二羰基单元，从而促进后者的化学和位点选择性醇解（请参阅方案）。该复合物激活了两个反应伙伴。此策略可在接近中性pH的条件下在加成/消除反应中裂解CC，CN和CO键，并为官能团转化提供了一种新方法。

  DOI：

  10.1002/anie.201200304
• 作为产物：
  描述：

  N-Boc-L-苯丙氨醇 在 氧气 、 高氯酸四乙基铵 作用下， 生成 (S)-3-(tert-butoxycarbonyl)-4-benzyl-2-oxazolidinone
  参考文献：
  名称：

  Electrogenerated Superoxide-Activated Carbon Dioxide. A New Mild and Safe Approach to Organic Carbamates

  摘要：

  The electrochemical reduction of O-2 (E = -1.0 V vs SCE) in dipolar aprotic solvents in the presence of CO2 gave a carboxylating reagent (O-2(.-)/CO2) able to convert amines and different types of their derivatives into carbamates. Primary and secondary aliphatic and aromatic amines were converted into the corresponding ethyl carbamates by the addition of EtI to the carbamate anions generated in the first step of the reactions. The yields were dependent on the nucleophilicity of the nitrogen atom. beta-Bromoethyl- and propylamine gave 2-oxazolidinone and tetrahydro-1,3-oxazin-2-one in moderate yields. N-Acyl or N-(alkoxycarbonyl)alkylamines bearing a leaving group at the beta position of the alkyl substituent were converted into 3-substituted-2-oxazolidinones in high yields. By using chiral substrates, enantiopure 3-alkoxycarbonyl(or acyl)-4-substituted oxazolidin-2-ones (70-85% isolated yields) were obtained. This represents a new mild and safe route to these important auxiliaries for asymmetric synthesis. Some limitations of the process are also evidenced and accounted for.

  DOI：

  10.1021/jo970308h

文献信息

• Simple and Efficient N-Acylation Reactions of Chiral Oxazolidine Auxiliaries
  作者：David J. Ager、David R. Allen、David R. Schaad

  DOI：10.1055/s-1996-4402

  日期：1996.11

  A simplified procedure for the N-acylation of oxazolidin-2-one chiral auxiliaries has been developed. The acylations occur at room temperature in the presence of triethylamine and catalytic quantities of 4-(N,N-dimethylamino)pyridine, thereby eliminating the necessity for a strong base such as butyllithium. Acylations with both symmetrical and mixed anhydrides, as well as acid chlorides, occur with a wide variety of oxazolidinone auxiliaries.

  已经开发了一种简化的程序用于N-酰化氧杂环丁烷-2-酮手性辅助剂。酰化在室温下进行，使用三乙胺和催化量的4-(N,N-二甲氨基)吡啶，从而消除了使用强碱（如丁基锂）的必要性。对对称和混合酸酐以及酸氯化物的酰化可以适用于多种氧杂环丁烷酮辅助剂。
• Substrate acidities and conversion times for reactions of amides with di-tert-butyl bicarbonate
  作者：Marvin M. Hansen、Allen R. Harkness、D. Scott Coffey、Frederick G. Bordwell、Yongyu Zhao

  DOI：10.1016/0040-4039(95)01931-7

  日期：1995.12

  The conversion time tor 4-dimethylaminopyndine catalysed reaction of amides with di-tert-butyl dicarbonate varies dramatically with substrate acidity. The pKa's in DMSO of some amides are determined to support correlation of reactivity with substrate acidity. Particularly acidic substrates, such as 4-thiazolidinone, readily react with a variety of dialkyl dicarbonates. Less acidic substrates react

  酰胺与四碳酸二叔丁酯的4-二甲基氨基吡啶催化的转化时间随底物酸度的变化而变化。的pK一个的在一些酰胺的DMSO被确定为与底物的反应性酸度的支持相关性。特别是酸性的底物，例如4-噻唑烷酮，很容易与各种二碳酸二烷基酯反应。酸性较低的底物与Boc 2 O反应，但其他二碳酸二烷基酯优先分解。
• A facile new method for selective deprotection of N-(tert-butoxycarbonyl)-protected carboxamides with Yb(OTf)3 supported on silica gel
  作者：Hiyoshizo Kotsuki、Takeshi Ohishi、Tomohiro Araki、Koji Arimura

  DOI：10.1016/s0040-4039(98)00950-2

  日期：1998.7

  A selective new method for the deprotection of N-Boc carboxamides was achieved by using Yb(OTf)(3), supported on silica gel under solvent-free conditions. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Electrogenerated Superoxide-Activated Carbon Dioxide. A New Mild and Safe Approach to Organic Carbamates
  作者：Maria Antonietta Casadei、Franco Micheletti Moracci、Giovanni Zappia、Achille Inesi、Leucio Rossi

  DOI：10.1021/jo970308h

  日期：1997.10.1

  The electrochemical reduction of O-2 (E = -1.0 V vs SCE) in dipolar aprotic solvents in the presence of CO2 gave a carboxylating reagent (O-2(.-)/CO2) able to convert amines and different types of their derivatives into carbamates. Primary and secondary aliphatic and aromatic amines were converted into the corresponding ethyl carbamates by the addition of EtI to the carbamate anions generated in the first step of the reactions. The yields were dependent on the nucleophilicity of the nitrogen atom. beta-Bromoethyl- and propylamine gave 2-oxazolidinone and tetrahydro-1,3-oxazin-2-one in moderate yields. N-Acyl or N-(alkoxycarbonyl)alkylamines bearing a leaving group at the beta position of the alkyl substituent were converted into 3-substituted-2-oxazolidinones in high yields. By using chiral substrates, enantiopure 3-alkoxycarbonyl(or acyl)-4-substituted oxazolidin-2-ones (70-85% isolated yields) were obtained. This represents a new mild and safe route to these important auxiliaries for asymmetric synthesis. Some limitations of the process are also evidenced and accounted for.
• Double Molecular Recognition with Aminoorganoboron Complexes: Selective Alcoholysis of β-Dicarbonyl Derivatives
  作者：Shunsuke Oishi、Susumu Saito

  DOI：10.1002/anie.201200304

  日期：2012.5.29

  Double duty: Aminoorganoboron (AOB) complexes recognize alcohol and β‐dicarbonyl units, and thereby facilitate chemo‐ and site‐selective alcoholysis of the latter (see scheme). The complex activates both reaction partners. This strategy enables CC, CN, and CO bond cleavage in addition/elimination reactions under near neutral pH conditions and provides a new method for functional group conversions

  双重职责：氨基有机硼酸盐（AOB）络合物识别醇和β-二羰基单元，从而促进后者的化学和位点选择性醇解（请参阅方案）。该复合物激活了两个反应伙伴。此策略可在接近中性pH的条件下在加成/消除反应中裂解CC，CN和CO键，并为官能团转化提供了一种新方法。