Diethyl (2S)-O-tert-butylmalate | 167971-72-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Diethyl (2S)-O-tert-butylmalate
• 英文别名: 2S-tert-Butoxy-succinic acid diethyl ester；diethyl (2S)-2-[(2-methylpropan-2-yl)oxy]butanedioate
• CAS: 167971-72-4
• 化学式: C₁₂H₂₂O₅
• 分子量: 246.304
• InChiKey: OCDCUDLTLYTFNP-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Diethyl (2S)-O-tert-butylmalate 在 lithium aluminium tetrahydride 、 盐酸羟胺 、 三乙胺 、 mercury(II) oxide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 12.25h， 生成 (3S)-3-tert-butoxy-3,4-dihydro-2H-pyrrole 1-oxide
  参考文献：
  名称：

  A Five-Membered Enantiopure Cyclic Nitrone from Malic Acid by Regioselective Oxidation of Cyclic Hydroxylamine. Synthesis of (1S,7S,8aR)-Octahydro-1,7-dihydroxyindolizine

  摘要：

  The chiral optically pure five-membered 3-tert-butoxy-1-pyrroline N-oxide (1) was synthesized by a convenient five-step procedure from diethyl L-malate. The key step is the regioselective HgO dehydrogenation of the N-hydroxypyrrolidine 6 obtained by double-nucleophilic displacement of a (bis)mesylate with hydroxylamine. A rationalization of the observed regioselectivity of the oxidation by studying the oxidation of a deuterated N-hydroxypyrrolidine 20 is reported. Nitrone 1 has been applied to the synthesis of a new (1S,7S,8aR)-1,7-dihydroxyindolizidine (28) via 1,3-dipolar cycloaddition strategies.

  DOI：

  10.1021/jo00120a016
• 作为产物：
  描述：

  L-苹果酸二乙酯 、 异丁烯 在 Amberlite H-15 作用下， 以 正己烷 为溶剂， 反应 6.0h， 以91%的产率得到Diethyl (2S)-O-tert-butylmalate
  参考文献：
  名称：

  A Five-Membered Enantiopure Cyclic Nitrone from Malic Acid by Regioselective Oxidation of Cyclic Hydroxylamine. Synthesis of (1S,7S,8aR)-Octahydro-1,7-dihydroxyindolizine

  摘要：

  The chiral optically pure five-membered 3-tert-butoxy-1-pyrroline N-oxide (1) was synthesized by a convenient five-step procedure from diethyl L-malate. The key step is the regioselective HgO dehydrogenation of the N-hydroxypyrrolidine 6 obtained by double-nucleophilic displacement of a (bis)mesylate with hydroxylamine. A rationalization of the observed regioselectivity of the oxidation by studying the oxidation of a deuterated N-hydroxypyrrolidine 20 is reported. Nitrone 1 has been applied to the synthesis of a new (1S,7S,8aR)-1,7-dihydroxyindolizidine (28) via 1,3-dipolar cycloaddition strategies.

  DOI：

  10.1021/jo00120a016

文献信息

• A New, Practical and Efficient Method for Protecting Alcohols as tert-Butyl Ethers
  作者：Ernesto Occhiato、Cristina Prandi、Alessandro Barge、Dina Scarpi、Silvia Tabasso、Paolo Venturello

  DOI：10.1055/s-0029-1219360

  日期：2010.3

  A new method for protecting alcohols as tert-butyl ethers is reported. The reaction is performed in tert-butyl acetate in the presence of a catalytic amount of HClO 4 . The process is extremely efficient and primary and secondary alcohols as well as diols are protected under very mild conditions. Remarkably, tert-butyl acetate can be easily recovered after the workup of the reaction and recycled.

  报道了一种将醇类保护为叔丁基醚的新方法。该反应在催化量的HClO 4 存在下在乙酸叔丁酯中进行。该过程非常有效，伯醇和仲醇以及二醇在非常温和的条件下得到保护。值得注意的是，乙酸叔丁酯在反应后很容易回收并循环使用。
• A Five-Membered Enantiopure Cyclic Nitrone from Malic Acid by Regioselective Oxidation of Cyclic Hydroxylamine. Synthesis of (1S,7S,8aR)-Octahydro-1,7-dihydroxyindolizine
  作者：Stefano Cicchi、Andrea Goti、Alberto Brandi

  DOI：10.1021/jo00120a016

  日期：1995.7

  The chiral optically pure five-membered 3-tert-butoxy-1-pyrroline N-oxide (1) was synthesized by a convenient five-step procedure from diethyl L-malate. The key step is the regioselective HgO dehydrogenation of the N-hydroxypyrrolidine 6 obtained by double-nucleophilic displacement of a (bis)mesylate with hydroxylamine. A rationalization of the observed regioselectivity of the oxidation by studying the oxidation of a deuterated N-hydroxypyrrolidine 20 is reported. Nitrone 1 has been applied to the synthesis of a new (1S,7S,8aR)-1,7-dihydroxyindolizidine (28) via 1,3-dipolar cycloaddition strategies.