(4R,5R)-4,5-Dimethyl-2-oxazolidinone | 159406-26-5

• 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: (4R,5R)-4,5-Dimethyl-2-oxazolidinone
• 英文别名: (4R,5R)-4,5-dimethyl-1,3-oxazolidin-2-one
• CAS: 159406-26-5
• 化学式: C₅H₉NO₂
• 分子量: 115.132
• InChiKey: DXRZFYKVFKAPCE-QWWZWVQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (5R)-4,5-dimethyl-1,3-oxazolidin-2-one 以91%的产率得到
  参考文献：
  名称：

  Zietlow Andrea, Steckhan Eberhard, J. Org. Chem., 59 (1994) N 19, S 5658-5661

  摘要：

  DOI：

文献信息

• Electrogenerated chiral building blocks for diastereoselective amidoalkylation reactions
  作者：P Brungs、K Danielmeier、J Jakobi、C Nothhelfer、A Stahl、A Zietlow、E Steckhan

  DOI：10.1051/jcp/1996930575

  日期：——

  Three different electrochemical methods have been applied for the synthesis of chiral building blocks for diastereoselective amidoalkylation reactions. These are A. the direct anodic α-methoxylation of amides and carbamates; B. anodic methoxylative decarboxylation of α-amino acid derivatives (Hofer-Moest reaction) C. indirect NaCl mediated anodic α-methoxylation of α-amino acid derivatives. The application of these building blocks for the synthesis of enantiomerically pure α-amino acids, dichiral 1,2-amino alcohols and chiral 1,3-diamines is described.

  已经应用了三种不同的电化学方法来合成用于二分立体选择性氨基烷基化反应的手性构建块。这些方法包括：A. 酰胺和碳酸酯的直接阳极α-甲氧基化；B. α-氨基酸衍生物的阳极甲氧基化脱羧（Hofer-Moest反应）C. 间接NaCl介导的α-氨基酸衍生物的阳极α-甲氧基化。描述了这些构建块在合成手性纯α-氨基酸、二分手性1,2-氨基醇和手性1,3-二胺中的应用。
• Diastereoselective Amidoalkylation Reactions of Electrochemically Methoxylated Chiral 2-Oxazolidinones with Organocopper Reagents
  作者：Andrea Zietlow、Eberhard Steckhan

  DOI：10.1021/jo00098a025

  日期：1994.9

  (4RS,5R)-4-Methoxy-5-methyl-2-oxazolidinone (2ab), easily obtained by electrochemical decarboxylative methoxylation of the cyclic L-threonine derivative (4S,5R)-5-methyl-2-oxzolidinone-4-carboxylic acid (1), acts as effective diastereoselective amidoalkylation reagent. The methoxy group exchange in 2ab can be performed with higher order organocuprates (R(3)Cu(2)Li) in the presence of BF3.OEt(2). The 4-alkyl- or 4-aryl-substituted 2-oxazolidinones 3-6 can be obtained with trans diastereoselectivities between 75 and 98% in S(N)1 fashion via the intermediate N-acylimine. On the contrary, the N-methylated (4RS,5R)-4-methoxy-3,5-dimethyl-2-oxzolidinone (7ab) undergoes methoxy group exchange under identical conditions mainly via the S(N)2 mechanism. Thus, starting from trans-7a mainly cis-8b is formed with 76% ds. The described procedures make cis- or trans-4-alkyl-5-methyl-2-oxazolidinones and the respective dichiral 2-amino alcohols selectively available by a short reaction sequence.

  (4RS,5R)-4-甲氧基-5-甲基-2-氧杂环丁酮 (2ab) 可通过电化学脱羧甲氧基化反应方便地由环状 L-苏糖衍生物 (4S,5R)-5-甲基-2-氧杂环丁酮-4-羧酸 (1) 制得，它作为一种高效的非对映选择性胺基烷基化试剂。2ab 中的甲氧基交换反应可以在 BF3.OEt2 的存在下使用更高价态的有机铜试剂 (R(3)Cu(2)Li) 进行。通过 N-酰亚胺中间体，在 S(N)1 机制下，以 75 到 98% 的反式非对映选择性可获得 4-烷基或 4-芳基取代的 2-氧杂环丁酮 3-6。相反，N-甲基化的 (4RS,5R)-4-甲氧基-3,5-二甲基-2-氧杂环丁酮 (7ab) 在相同条件下主要通过 S(N)2 机制进行甲氧基交换。因此，从反式-7a 主要生成顺式-8b，非对映选择性为 76%。所述的程序通过短反应序列，选择性地提供顺式或反式的 4-烷基-5-甲基-2-氧杂环丁酮及其相应的双手性 2-氨基醇。