3-hydroxy-6-methyl-6-heptenoic acid ethyl ester | 156556-28-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: 3-hydroxy-6-methyl-6-heptenoic acid ethyl ester
• 英文别名: Ethyl 3-hydroxy-6-methylhept-6-enoate
• CAS: 156556-28-4
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: UYUJMTZRSJREQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  3-hydroxy-6-methyl-6-heptenoic acid ethyl ester 在 甲醇 、 4-二甲氨基吡啶 、 二甲基硫 、 氧气 、 1,8-双二甲氨基萘 、 臭氧 、 N,N-二异丙基乙胺 、 对甲苯磺酰氯 、 sodium hydroxide 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 生成 2-methoxy-5-methyl-6-oxabicyclo[3.2.0]heptan-7-one
  参考文献：
  名称：

  A Diastereoselective, Nucleophile-Promoted Aldol-Lactonization of Ketoacids Leading to Bicyclic-β-Lactones

  摘要：

  An improved, tandem acid activation/aldol-lactonization process is described. This more practical protocol shortens reaction times for the construction of bicyclic beta-lactones from ketoacids and implements the use of commercially available reagents p-toluenesulfonyl chloride (p-TsC1) as activator and 4-dimethylaminopyridine (4-DMAP) as nucleophllic promoter (Lewis base). Substrates with beta-substituents, with respect to the carboxylic acid, consistently showed excellent levels of diastereoselectivity during the bis-cyclization event.

  DOI：

  10.1021/jo202252y
• 作为产物：
  描述：

  ethyl 6-methyl-3-oxohept-6-enoate 在 氢氧化钾 作用下， 生成 3-hydroxy-6-methyl-6-heptenoic acid ethyl ester
  参考文献：
  名称：

  贝克酵母还原法合成三官能（R）-3-羟基酯的对映体特异性

  摘要：

  对映体纯的三官能（R）-3-羟基酯（7）–（10）的不对称合成可以通过面包酵母还原水解的β-酮羧酸盐（2）–（5）来实现，而不是通过还原相应的酯。

  DOI：

  10.1039/c39830000599

文献信息

• Practical preparation of bicyclo[3.2.0]hept-3-en-6-ones and its utilisation in stereoselective total synthesis of grandisol and lineatin via a versatile intermediate.
  作者：Giovanni Confalonieri、Emanuela Marotta、Franco Rama、Paolo Righi、Goffredo Rosini、Rossella Serra、Francesca Venturelli

  DOI：10.1016/s0040-4020(01)81119-4

  日期：1994.3

  devised for racemic grandisol and lineatin, two important components of pheromonic blends. They are based on the utilisation of 1,4-dimethylbicyclo[3.2.0]hept-3-en-6-one as a pivotal intermediate. This compound, as well as other bicyclo[3.2.0]hept-3-en-6-ones, are now easily available by a practical bicyclization of the corresponding 3-hydroxy-6-alkenoic acids.

  已经为外消旋的香兰地松和利奈汀（信息素混合物的两个重要组成部分）设计了新的有效的立体选择性总合成物。它们基于利用1，4-二甲基双环[3.2.0] hept-3-en-6-one作为关键中间体。该化合物以及其他双环[3.2.0]庚-3-烯-6-酮现在可以通过相应的3-羟基-6-链烯酸的实际双环化反应轻松获得。
• Synthesis of methyl substituted bicyclo[3.2.0]hept-3-en-6-ones and 3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-ones.
  作者：Emanuela Marotta、Ilaria Pagani、Paolo Righi、Goffredo Rosini

  DOI：10.1016/s0040-4020(01)90491-0

  日期：——

  performed on bicyclo[3.2.0]hept-3-en-6-ones and on bicyclo[3.2.0]hept-2-en-6-one. 3,3a,4,6a-Tetrahydro-2H-cyclopenta[b]furan-2-ones, important starting materials in the synthesis of linear condensed triquinane sesquiterpenes, have been prepared in an efficient manner by the easy bicyclization of 3-hydroxy-6-heptenoic acids, followed by a Baeyer-Villiger oxidation of the bicyclo[3.2.0]hept-3-en-6-one

  在乙酸酐和乙酸钾中处理甲基单或双取代的3-羟基-6-链烯酸，可得到相当好的收率的相应双环[3.2.0] hept-3-en-6-one。该反应似乎普遍适用于五元环的所有部分中的甲基衍生物。通过3-羟基-3-甲基-6-庚烯酸的有效双环化反应，然后通过双羟甲基化3-羟基-3-甲基-6-庚烯酸，合成4,7,7-三甲基双环[3.2.0] hept-3-en-6-one（filifolone）报道了中间体4-甲基双环[3.2.0lhept-3-en-6-one。当在双环[3.2.0]庚-3-en-6-one和双环[3.2.0]庚-2-en-6-one上进行时，后一种反应被证明是通用方法。3,3a，4,6a-四氢-2 H-环戊[ b呋喃-2-酮是线性缩合的三喹烷倍半萜烯合成中的重要起始原料，它是通过3-羟基-6-庚烯酸的简单双环化反应，然后通过双环的Baeyer-Villiger氧化反应，以有效的方式制备的。
• Enantiospecific syntheses of trifunctional (R)-3-hydroxy esters by baker's yeast reduction
  作者：Masahiro Hirama、Mitsuaki Shimizu、Mitsuko Iwashita

  DOI：10.1039/c39830000599

  日期：——

  Asymmetric syntheses of the enantiomerically pure trifunctional (R)-3-hydroxy esters (7)–(10) can be achieved by baker's yeast reduction of the hydrolysed β-keto carboxylates (2)–(5) instead of by reduction of the corresponding ester.

  对映体纯的三官能（R）-3-羟基酯（7）–（10）的不对称合成可以通过面包酵母还原水解的β-酮羧酸盐（2）–（5）来实现，而不是通过还原相应的酯。
• A Diastereoselective, Nucleophile-Promoted Aldol-Lactonization of Ketoacids Leading to Bicyclic-β-Lactones
  作者：Gang Liu、Morgan E. Shirley、Daniel Romo

  DOI：10.1021/jo202252y

  日期：2012.3.2

  An improved, tandem acid activation/aldol-lactonization process is described. This more practical protocol shortens reaction times for the construction of bicyclic beta-lactones from ketoacids and implements the use of commercially available reagents p-toluenesulfonyl chloride (p-TsC1) as activator and 4-dimethylaminopyridine (4-DMAP) as nucleophllic promoter (Lewis base). Substrates with beta-substituents, with respect to the carboxylic acid, consistently showed excellent levels of diastereoselectivity during the bis-cyclization event.