(R)-4-Ethyl-2-methoxy-3-tosyl-1,3-oxazolidine

• 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: (R)-4-Ethyl-2-methoxy-3-tosyl-1,3-oxazolidine
• 英文别名: (2RS,4R)-4-Ethyl-2-methoxy-3-tosyl-1,3-oxazolidine；(4R)-4-ethyl-2-methoxy-3-(4-methylphenyl)sulfonyl-1,3-oxazolidine
• 化学式: C₁₃H₁₉NO₄S
• 分子量: 285.364
• InChiKey: HTVRBZKBONLYMN-JTDNENJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-4-Ethyl-2-methoxy-3-tosyl-1,3-oxazolidine 在 zinc chloride diethyl ether 、 三乙胺 、 lithium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 124.0h， 生成 (2R,4R)-4-Ethyl-2-((Z)-2-phenyl-2-trimethylsilanyloxy-vinyl)-3-(toluene-4-sulfonyl)-oxazolidine
  参考文献：
  名称：

  Enantio- and Diastereoselective Synthesis of (Protected) 2-Formyl- and 2-(Hydroxymethyl)-1-phenylalkane-1,3-diols from Chiral 2-Methoxy-3-tosyl-1,3-oxazolidines by Subsequent Asymmetric Formylation and Aldolization

  摘要：

  三甲基硅基烯醇醚通过与2-甲氧基-1,3-噁唑啉-2的非对称甲醛化反应，依次转化为具有手性保护的α-甲酰基酮，随后转化为相应的热力学确定的(Z)-TMS烯醇醚，再与醛类发生缩合。所有步骤均具有较高的立体选择性。文中对中间体8中的三种不同氧官能团所带来的合成选择进行了阐述，以便为目标化合物提供合成途径。

  DOI：

  10.1055/s-2000-6393

文献信息

• Asymmetric Synthesis of Stereodefined 7-(Alk-1-enyl)-5,6,7,8-tetrahydronaphthalene-2-carboxylic Acids and Their Precursors, Bearing a Polar Group in the 8-Position, by the 3-Sulfonyl-1,3-oxazolidine Method
  作者：Antje Kreier、Roland Fröhlich、Elina Wegelius、Dieter Hoppe

  DOI：10.1055/s-2000-7119

  日期：——

  7-Bromo-1-(trimethylsilyloxy)-naphthalene 2 was subjected to asymmetric formylation by means of (R)-4-ethyl-2-methoxy-3-tosyl-1,3-oxazolidine (1). The enantiomerically pure 1-tetralones u-3 and l-3, bearing a masked formyl group, were elaborated diastereoselectively to achieve the title compounds 11, 13 and 23 by transformation of the 1-oxo group to a tertiary methyl carbinol moiety or a hydroxymethyl group. Subsequently, the formyl group was converted to a long-chain alkene moiety and, finally, the carboxyl group was introduced via bromine-lithium exchange and carboxylation. Difficulties arose from the high dehydration tendencies of the intermediate tertiary alcohols and by facile epimerisation of the free hydroxyaldehydes. With examples for further application of similar strategies it is demonstrated how these problems could be solved.

  7-溴-1-(三甲基硅氧基)-萘 2 通过 (R)-4-乙基-2-甲氧基-3-托斯酰基-1,3-噁唑烷 (1) 进行不对称的形式化。在具有掩蔽形式基团的对映体纯的 1-四氢萘酮 u-3 和 l-3 的基础上，通过将 1-氧基转化为三级甲基醇或羟甲基团，选择性地合成了目标化合物 11、13 和 23。随后，形式基团被转化为长链烯烃，最后通过溴-锂交换和羧基化引入了羧基。中间三级醇的高脱水倾向以及游离羟醛的易表异构化导致了一些困难。通过类似策略的进一步应用实例，展示了解决这些问题的方法。
• Enantio- and Diastereoselective Synthesis of (Protected) 2-Formyl- and 2-(Hydroxymethyl)-1-phenylalkane-1,3-diols from Chiral 2-Methoxy-3-tosyl-1,3-oxazolidines by Subsequent Asymmetric Formylation and Aldolization
  作者：Frank Steif、Birgit Wibbeling、Oliver Meyer、Dieter Hoppe

  DOI：10.1055/s-2000-6393

  日期：——

  Trimethylsilyl enol ethers are successively converted into chirally protected α-formyl ketones by asymmetric formylation with the 2-methoxy-1,3-oxazolidine 2, transformed into the corresponding, thermodynamically determined (Z)-TMS enol ethers, and then are allowed to condense with aldehydes. All steps proceed with high stereoselectivity. Some synthetic options, arising from the three differentiated oxygen functionalities in the intermediates 8 are illustrated for the title target compounds.

  三甲基硅基烯醇醚通过与2-甲氧基-1,3-噁唑啉-2的非对称甲醛化反应，依次转化为具有手性保护的α-甲酰基酮，随后转化为相应的热力学确定的(Z)-TMS烯醇醚，再与醛类发生缩合。所有步骤均具有较高的立体选择性。文中对中间体8中的三种不同氧官能团所带来的合成选择进行了阐述，以便为目标化合物提供合成途径。