ethyl (5S)-5-hydroxy-2-hexenoate | 188924-78-9

• 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: ethyl (5S)-5-hydroxy-2-hexenoate
• 英文别名: (S,E)-ethyl 5-hydroxyhex-2-enoate；ethyl (E,5S)-5-hydroxyhex-2-enoate
• CAS: 188924-78-9
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: ZVXVRZZECWGGIC-KNIZRNDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  ethyl (5S)-5-hydroxy-2-hexenoate 在 四氧化锇 、 Hydroquinone 1,4-phthalazinediyl diether 甲基磺酰胺 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 叔丁醇 为溶剂， 生成 (2R,3S,5S)-ethyl 2,3,5-trihydroxy-hexanoate
  参考文献：
  名称：

  De Novo Enantioselective Syntheses of Galacto-Sugars and Deoxy Sugars via the Iterative Dihydroxylation of Dienoate

  摘要：

  [GRAPHICS]An efficient route to various sugar lactones has been developed. Key to the overall transformation is the sequential osmium-catalyzed dihydroxylation of 2,4-dienoates. The simplest (one-step/racemic) example of this reaction occurs when the dihydroxylation is performed with aqueous NMO in MeOH. When the first dihydroxylation is performed using the AD-mix procedure, an enantioselective variant results. When a matched AD-mix procedure is used for the second dihydroxylation, an exceedingly diastereo- and enantioselective synthesis of galacto-1,4-lactone results.

  DOI：

  10.1021/ol050044i
• 作为产物：
  描述：

  山梨酸乙酯 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 甲基磺酰胺 、 potassium carbonate 吡啶 、 四氧化锇 、 甲酸 、 (DHQ)2-PHAL 、 三乙胺 、 三苯基膦 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 4.5h， 生成 ethyl (5S)-5-hydroxy-2-hexenoate
  参考文献：
  名称：

  对乙酰氯三乙酸酯，隐香烯酮和隐香烯酮双乙酸酯的对映选择性合成。

  摘要：

  [反应：见正文]来自山茱rypto的三种天然产物的对映选择性合成是从山梨酸乙酯经过13到15步完成的。该路线依赖于对映体和区域选择性的Sharpless二羟基化反应和钯催化的还原反应，以建立绝对的立体化学。该路线还依赖于高度（E）-选择性的烯烃交叉复分解反应以形成反式-δ-羟基-1-烯酸酯。随后将所得的δ-羟基-1-烯酸酯转化为隐乙酸三乙酸酯，隐caryolone和双隐隐caryolone。

  DOI：

  10.1021/ol0345529

文献信息

• Asymmetric, Catalytic, and Direct Self-Aldol Reaction of Acetaldehyde Catalyzed by Diarylprolinol
  作者：Yujiro Hayashi、Sampak Samanta、Takahiko Itoh、Hayato Ishikawa

  DOI：10.1021/ol802438u

  日期：2008.12.18

  An asymmetric, catalytic, and direct self-aldol reaction of acetaldehyde was catalyzed by diarylprolinol in NMP, affording the trimer acetal, which was generated by the reaction of the self-aldol product with another acetaldehyde molecule in a moderate yield with good enantioselectivity. Acetal is the synthetic equivalent of the self-aldol product, which can be converted into other synthetically useful

  二芳基脯氨醇在NMP中催化乙醛的不对称，催化和直接的自身醛醇缩合反应，得到三聚体乙缩醛，它是通过自身醛醇产物与另一个乙醛分子以中等收率和良好的对映选择性反应而生成的。乙缩醛是自醛醇缩合产物的合成等同物，可以在一个罐中将其转化为其他合成有用的化合物，而不会损害对映选择性。
• Enantioselective Syntheses of Cryptocarya Triacetate, Cryptocaryolone, and Cryptocaryolone Diacetate
  作者：Catherine M. Smith、George A. O'Doherty

  DOI：10.1021/ol0345529

  日期：2003.5.1

  products from Cryptocarya latifolia have been achieved in 13-15 steps from ethyl sorbate. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to establish the absolute stereochemistry. The route also relies upon a highly (E)-selective olefin cross-metathesis reaction to form trans-delta-hydroxy-1-enoates. The resulting delta-hydroxy-1-enoates were

  [反应：见正文]来自山茱rypto的三种天然产物的对映选择性合成是从山梨酸乙酯经过13到15步完成的。该路线依赖于对映体和区域选择性的Sharpless二羟基化反应和钯催化的还原反应，以建立绝对的立体化学。该路线还依赖于高度（E）-选择性的烯烃交叉复分解反应以形成反式-δ-羟基-1-烯酸酯。随后将所得的δ-羟基-1-烯酸酯转化为隐乙酸三乙酸酯，隐caryolone和双隐隐caryolone。
• An Enantioselective Synthesis of Cryptocarya Diacetate
  作者：Thomas J. Hunter、George A. O'Doherty

  DOI：10.1021/ol016399t

  日期：2001.8.1

  enantioselective synthesis of cryptocarya diacetate has been achieved in 10 steps from ethyl sorbate. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to form a delta-hydroxy-1-enoate, which was subsequently converted into a benzylidene-protected 3,5-dihydroxy carboxylic ester. This ester was converted into cryptocarya diacetate in 14% overall

  [反应：请参见文字]。由山梨酸乙酯分十步完成了隐乙酸二乙酸酯的对映选择性合成。该途径依赖于对映体和区域选择性的Sharpless二羟基化和钯催化的还原以形成δ-羟基-1-烯酸酯，其随后被转化为亚苄基保护的3，5-二羟基羧酸酯。通过烯丙基化和复分解环闭合反应序列，该酯以14％的总产率转化为隐乙酸二乙酸酯。
• De novo asymmetric syntheses of C-4-substituted sugars via an iterative dihydroxylation strategy
  作者：Md. Moinuddin Ahmed、George A. O’Doherty

  DOI：10.1016/j.carres.2006.03.024

  日期：2006.7

  highly efficient route to various C-4 substituted sugar lactones has been developed. The key to the overall transformation is the sequential osmium-catalyzed dihydroxylation reaction of substituted 2,4-dienoates and an allylic substitution at the C-4 position. When the Sharpless AD-mix procedure is used in a matched sense for the second dihydroxylation reaction, it results in an exceedingly diastereo-

  已经开发了一种短且高效的途径来制备各种C-4取代的糖内酯。总体转化的关键是取代的2，4-二烯酸酯的催化的二羟基化反应和C-4位置的烯丙基取代。当将Sharpless AD-mix程序以匹配的方式用于第二个二羟基化反应时，会导致几种C-4取代糖的非对映和对映选择性合成。
• An Enantioselective Synthesis of Benzylidene-Protected <i>syn</i>-3,5-Dihydroxy Carboxylate Esters via Osmium, Palladium, and Base Catalysis
  作者：Thomas J. Hunter、George A. O'Doherty

  DOI：10.1021/ol0156188

  日期：2001.4.1

  [GRAPHICS]The enantioselective syntheses of several protected syn-3,5-dihydroxy carboxylic esters have been achieved from the corresponding achiral 1,3-dieneoates, The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to form delta -hydroxy-1-enoates, The resulting delta -hydroxy-1-enoates are subsequently converted into benzylidene-protected 3,5-dihydroxy carboxylic esters in one step, The benzylidene-protected 3,5-dihydroxy carboxylic esters are produced in good overall yields (25% to 51%) and high enantiomeric excesses (80% to >95%).