(4R,5R)-4-methyl-5-hydroxyhex-2(E)-enoic acid benzyl ester | 206762-52-9

• 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: (4R,5R)-4-methyl-5-hydroxyhex-2(E)-enoic acid benzyl ester
• 英文别名: (+)-benzyl (4R,5R,E)-5-hydroxy-4-methyl-2-hexenoate；benzyl (E,4R,5R)-5-hydroxy-4-methylhex-2-enoate
• CAS: 206762-52-9
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: UVCQJYDJEFONIU-SVKHLYGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  (4R,5R)-4-methyl-5-hydroxyhex-2(E)-enoic acid benzyl ester 在 咪唑 、 碘 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以37%的产率得到(4R,5R)-5-iodo-4-methyl-hex-2(E)-enoic acid benzyl ester
  参考文献：
  名称：

  Investigation of SmI2-mediated cyclisation of δ-iodo-α,β-unsaturated esters by deuterium 2D NMR in oriented solvents

  摘要：

  We have investigated the mechanism of the SmI2-mediated cyclisation of delta-iodo-alpha,beta-unsaturated esters using proton-decoupled deuterium 1D and 2D NMR in weakly ordered polypeptide liquid crystal solvents. Analysis of the spectroscopic results demonstrates that the cyclisation reaction takes place with concomitant and extensive racemisation at the gamma-position and the reason for this racemisation is discussed. We also report an efficient 2D NMR strategy for distinguishing meso- from d- and l-diastereoisomers based on the introduction of a CD2 probe in the molecules to be studied. This approach allows determination of the diastereoisomeric and enantiomeric composition of a mixture. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00259-8
• 作为产物：
  描述：

  (E)-2-methyl-2-buten-1-ol 在 titanium(IV) isopropylate 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 四丙基高钌酸铵 甲酸 、 三丁基膦 、 过氧化氢异丙苯 、 3 A molecular sieve 、 4 A molecular sieve 、 D-(-)-酒石酸二异丙酯 、 N-甲基吗啉氧化物 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 乙腈 为溶剂， 反应 26.5h， 生成 (4R,5R)-4-methyl-5-hydroxyhex-2(E)-enoic acid benzyl ester
  参考文献：
  名称：

  海洋天然产物合成中的钯催化的分子内烯丙基烷基化反应：（+）-Pederate的对映选择性合成，Mycalamides合成的关键中间体。

  摘要：

  描述了一种新的制备方法，该方法制备了（+）-山酸甲酯（4），它是合成Mycalamides（1）的关键中间体，而mycalamides（1）是来自Mycale属新西兰海绵的海洋天然产物。关键步骤涉及衍生自（+）-（4R，5R，E）-5-（叔丁基二甲基甲硅烷氧基）-4-甲基-2-己烯醇（13）的钯催化的碳酸酯21的分子内烯丙基烷基化反应，生成内酯5，收率87％。环化产物5的脱甲氧基羰基化和进一步的官能团转化导致（+）-山ped酸甲酯（4）。

  DOI：

  10.1021/jo9805246

文献信息

• A Practical Synthesis of the Key Intermediate for Theopederins—An Enantioselective Total Synthesis of (+)-Methyl Pederate
  作者：Masahiro Toyota、Youichi Nishikawa、Keiichiro Fukumoto

  DOI：10.3987/com-97-s(n)104

  日期：——

  A practical synthesis of the key intermediate for theopederins, methyl pederate (15), has been accomplished by means of palladium-catalyzed reactions.
• Palladium-Catalyzed Intramolecular Allylic Alkylation Reaction in Marine Natural Product Synthesis:  Enantioselective Synthesis of (+)-Methyl Pederate, a Key Intermediate in Syntheses of Mycalamides
  作者：Masahiro Toyota、Masako Hirota、Youichi Nishikawa、Keiichiro Fukumoto、Masataka Ihara

  DOI：10.1021/jo9805246

  日期：1998.8.1

  A novel preparation of (+)-methyl pederate (4), a key intermediate in syntheses of mycalamides (1), marine natural products from a New Zealand sponge of the genus Mycale, is described. The key step involves palladium-catalyzed intramolecular allylic alkylation of the carbonate 21, derived from (+)-(4R,5R,E)-5-(tert-butyldimethylsiloxy)-4-methyl-2-hexenol (13), yielding lactones 5 in 87% yield. Demethoxycarbonylation

  描述了一种新的制备方法，该方法制备了（+）-山酸甲酯（4），它是合成Mycalamides（1）的关键中间体，而mycalamides（1）是来自Mycale属新西兰海绵的海洋天然产物。关键步骤涉及衍生自（+）-（4R，5R，E）-5-（叔丁基二甲基甲硅烷氧基）-4-甲基-2-己烯醇（13）的钯催化的碳酸酯21的分子内烯丙基烷基化反应，生成内酯5，收率87％。环化产物5的脱甲氧基羰基化和进一步的官能团转化导致（+）-山ped酸甲酯（4）。
• Investigation of SmI2-mediated cyclisation of δ-iodo-α,β-unsaturated esters by deuterium 2D NMR in oriented solvents
  作者：Hélène Villar、François Guibé、Christie Aroulanda、Philippe Lesot

  DOI：10.1016/s0957-4166(02)00259-8

  日期：2002.8

  We have investigated the mechanism of the SmI2-mediated cyclisation of delta-iodo-alpha,beta-unsaturated esters using proton-decoupled deuterium 1D and 2D NMR in weakly ordered polypeptide liquid crystal solvents. Analysis of the spectroscopic results demonstrates that the cyclisation reaction takes place with concomitant and extensive racemisation at the gamma-position and the reason for this racemisation is discussed. We also report an efficient 2D NMR strategy for distinguishing meso- from d- and l-diastereoisomers based on the introduction of a CD2 probe in the molecules to be studied. This approach allows determination of the diastereoisomeric and enantiomeric composition of a mixture. (C) 2002 Elsevier Science Ltd. All rights reserved.