(E,4S,5S)-ethyl 6-(benzyloxy)-4,5-dihydroxyhex-2-enoate | 848566-19-8

• 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: (E,4S,5S)-ethyl 6-(benzyloxy)-4,5-dihydroxyhex-2-enoate
• 英文别名: ethyl (E,4S,5S)-4,5-dihydroxy-6-phenylmethoxyhex-2-enoate
• CAS: 848566-19-8
• 化学式: C₁₅H₂₀O₅
• 分子量: 280.321
• InChiKey: GRXHNZOXJNIXKZ-CFYKVZDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E,4S,5S)-ethyl 6-(benzyloxy)-4,5-dihydroxyhex-2-enoate 在 氯化亚砜 、 三氟化硼乙醚 、 甲基锂 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.33h， 生成 (2E,4E)-ethyl 6-(benzyloxy)hexa-2,4-dienoate
  参考文献：
  名称：

  Addition of organocopper reagents to cyclic sulfites or carbonates of γ,δ-dihydroxy (E)-α,β-enoates

  摘要：

  Reaction of cyclic sulfites or carbonates of gamma,delta-dihydroxy (E)-alpha,beta-enoates with R2Cu(CN)Li2, BF3; RCu(CN)Li, BF3 (R = Me-,n-Bu-)afforded either diastereoselective S(N)2' products or reductive elimination product depending on reaction conditions. Addition of R2Cu(CN)Li2, BF3 (R = Me-, n-Bu-) to cyclic sulfite (1) or cyclic carbonate (3) (inverse addition) afforded highly regio-, (E)-stereo- and diastereoselectively alpha-alkylation products (6 and 8). By using this methodology, (2S, 5S)-trans-2-methyl-5-hexanolide, the pheromone of the carpenter bee Xylocopa hirutissima was synthesized.

  DOI：

  10.1016/s0957-4166(00)80506-6
• 作为产物：
  描述：

  (4S,5R)-4-benzyloxymethyl-2,2-dimethyl-1,3-dioxolane-5-carboxaldehyde 在 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 4.0h， 生成 (E,4S,5S)-ethyl 6-(benzyloxy)-4,5-dihydroxyhex-2-enoate
  参考文献：
  名称：

  Addition of organocopper reagents to cyclic sulfites or carbonates of γ,δ-dihydroxy (E)-α,β-enoates

  摘要：

  Reaction of cyclic sulfites or carbonates of gamma,delta-dihydroxy (E)-alpha,beta-enoates with R2Cu(CN)Li2, BF3; RCu(CN)Li, BF3 (R = Me-,n-Bu-)afforded either diastereoselective S(N)2' products or reductive elimination product depending on reaction conditions. Addition of R2Cu(CN)Li2, BF3 (R = Me-, n-Bu-) to cyclic sulfite (1) or cyclic carbonate (3) (inverse addition) afforded highly regio-, (E)-stereo- and diastereoselectively alpha-alkylation products (6 and 8). By using this methodology, (2S, 5S)-trans-2-methyl-5-hexanolide, the pheromone of the carpenter bee Xylocopa hirutissima was synthesized.

  DOI：

  10.1016/s0957-4166(00)80506-6

文献信息

• Palladium-catalyzed stereospecific epoxide-opening reaction of γ,δ-epoxy-α,β-unsaturated esters with an alkylboronic acid leading to γ,δ-vicinal diols with double inversion of the configuration
  作者：Atsushi Hirai、Xiao-Qiang Yu、Terumichi Tonooka、Masaaki Miyashita

  DOI：10.1039/b307390d

  日期：——

  A palladium-catalyzed stereospecific epoxide-opening reaction of gamma,delta-epoxy-alpha,beta-unsaturated esters with an alkylboronic acid leading to gamma,delta-vicinal diols is described, which proceeds with retention of the configuration, i.e., via two consecutive S(N)2 processes, to afford the corresponding gamma,delta-cyclic boronates in high yields.

  描述了γ-δ-环氧-α-β-不饱和酯与烷基硼酸的钯催化的立体有择环氧化物开环反应，生成γ-δ-邻位二醇，该反应继续保持构型，即通过两个连续的S（N）2的过程，以高收率提供相应的γ，δ环硼酸盐。
• 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。
• Palladium-catalyzed Stereospecific Epoxide-opening Reaction of γ,δ-Epoxy-α,β-unsaturated Esters with Boric Acid Leading to γ,δ-Diol Derivatives with Double Inversion of Configuration
  作者：Xiao-Qiang Yu、Atsushi Hirai、Masaaki Miyashita

  DOI：10.1246/cl.2004.764

  日期：2004.6

  A new palladium-catalyzed epoxide-opening reaction of γ,δ-epoxy-α,β-unsaturated esters with boric acid has been developed, which proceeds stereospecifically giving rise to the corresponding γ,δ-dio...

  已经开发了一种新的钯催化的 γ,δ-环氧-α,β-不饱和酯与硼酸的环氧化物开环反应，该反应进行立体定向，生成相应的 γ,δ-二...
• De novo synthesis of galacto-sugar δ-lactones via a catalytic osmium/palladium/osmium reaction sequence
  作者：Md. Moinuddin Ahmed、George A. O’Doherty

  DOI：10.1016/j.tetlet.2005.03.029

  日期：2005.4

  A highly efficient route to various 1,5-galacto-sugar lactones from dienoates has been developed by using three catalytic reactions. These reactions include (i) an enantioselective osmium-catalyzed dihydroxylation, (ii) a regio- and diastereoselective palladium-catalyzed pi-allyl alkylation with p-methoxyphenol for alcohol differentiation and protection, and (iii) a diastereoselective dihydroxylation that can be improved using matched emantioselective osmium-catalyzed dihydroxylation condition. (c) 2005 Elsevier Ltd. All rights reserved.
• De Novo Enantioselective Syntheses of <i>Galacto</i>-Sugars and Deoxy Sugars via the Iterative Dihydroxylation of Dienoate
  作者：Md. Moinuddin Ahmed、Bryan P. Berry、Thomas J. Hunter、Dennis J. Tomcik、George A. O'Doherty

  DOI：10.1021/ol050044i

  日期：2005.2.1

  [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.