(2E,4E)-ethyl 6-hydroxy-3-methylhexa-2,4-dienoate | 88714-53-8

• 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: (2E,4E)-ethyl 6-hydroxy-3-methylhexa-2,4-dienoate
• 英文别名: ethyl (2E,4E)-6-hydroxy-3-methylhexa-2,4-dienoate
• CAS: 88714-53-8
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: YHJOSAHZRXBLLI-AOSYACOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  (2E,4E)-ethyl 6-hydroxy-3-methylhexa-2,4-dienoate 在 咪唑 、 manganese(IV) oxide 、 正丁基锂 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.5h， 生成 tert-Butyl-[(2E,4E,6Z,8E)-4,7-dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraenyloxy]-dimethyl-silane
  参考文献：
  名称：

  Experimental and Theoretical Analysis of the Steric Tolerance of the Binding Site of Bacterioopsin with the Use of Side-Chain Methyl-Shifted Retinal Analogs

  摘要：

  Four positional isomers of trans-retinal (1) differing in the location of the side-chain methyl groups have been prepared by a combination of Wittig and highly stereocontrolled Suzuki coupling reactions. The incubation of 9-demethyl-10-methylretinal (5) with bacterioopsin yielded an artificial pigment with an opsin shift of 4630 cm(-1) The other three analogs, namely 13-demethyl-14-methylretinal (3), 13-demethyl-12-methylretinal (4), and 9-demethyl-8-methylretinal (6) did not bind to the apoprotein. In order to rationally address the intrinsic structural differences among analogs which could be relevant to the discrimination exhibited by the protein binding site, ab initio calculations with complete optimization at the 3-21G level were performed on model N-methylretinal iminium salts derived from aldehydes 1 and 3-6. The validity of the approach was inferred from the remarkable coincidence between the minimized structure of N-methylretinal Schiff base (PSB-1) and the structural parameters displayed by N-methyl-N-phenylretinal iminium perchlorate (38b). Computations clearly show that the location of the methyl groups on the polyene side chain is of the utmost importance in determining the overall shape of the retinal ligands. Those structural effects, added to the dominant steric and electronic restrictions of the binding pocket, would explain the observed discrimination among the analogs 3-6, with minor structural changes, and perhaps among other retinals reported in the literature. Additionally, the theoretical and experimental results obtained with 9-demethyl-8-methylretinal (6) provide further indirect evidence of the importance of the 6-s-trans conformation for the native chromophore in bacteriorhodopsin.

  DOI：

  10.1021/ja00136a021
• 作为产物：
  描述：

  3-甲酰基-2-丁烯酸乙酯 在 sodium tetrahydroborate 作用下， 以 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 15.33h， 生成 (2E,4E)-ethyl 6-hydroxy-3-methylhexa-2,4-dienoate
  参考文献：
  名称：

  一种新颖的催化不对称路线，向带有甲基取代的中心立体碳的跳过二烯。

  摘要：

  开发了一种高效的方法，该方法通过铜催化的二烯溴化物的不对称烯丙基烷基化反应，用甲基取代的中心立体碳对映选择性合成1,4-二烯（跳过的二烯）。在广泛的底物范围内，可实现出色的区域选择性和对映体选择性（高达SN2'/ SN2比为97：3，ee为99％）。

  DOI：

  10.1039/c3cc41021h

文献信息

• Total Synthesis of Etnangien
  作者：Pengfei Li、Jun Li、Fatih Arikan、Wiebke Ahlbrecht、Michael Dieckmann、Dirk Menche

  DOI：10.1021/ja9056163

  日期：2009.8.26

  The first total synthesis of the potent RNA-polymerase inhibitor etnangien is described, which establishes unequivocally the relative and absolute configuration of this sensitive macrolide antibiotic. Key features of the expedient and modular synthesis include stereoselective substrate-controlled boron- and tin-mediated aldol couplings to set the characteristic sequences of methyl and hydroxyl bearing

  描述了强效 RNA 聚合酶抑制剂 etnangien 的首次全合成，它明确确定了这种敏感的大环内酯类抗生素的相对和绝对构型。方便和模块化合成的关键特征包括立体选择性底物控制的硼和锡介导的羟醛偶联，以设置具有高度立体选择性和产率的甲基和羟基立体中心的特征序列，构象受限底物的有效 ​​Heck 大环化，以及不稳定侧链的后期引入。收敛方法应该适合设计的类似物。
• Stereoselective Total Synthesis of Etnangien and Etnangien Methyl Ester
  作者：Pengfei Li、Jun Li、Fatih Arikan、Wiebke Ahlbrecht、Michael Dieckmann、Dirk Menche

  DOI：10.1021/jo100201f

  日期：2010.4.16

  A highly stereoselective joint total synthesis of the potent polyketide macrolide antibiotics etnangien and etnangien methyl ester was accomplished by a convergent strategy and proceeds in 23 steps (longest linear sequence). Notable synthetic features include a sequence of highly stereoselective substrate-controlled aldol reactions to set the characteristic assembly of methyl- and hydroxyl-bearing

  有效的聚酮化合物大环内酯类抗生素etnangien和etnangien甲酯的高度立体选择性联合全合成通过收敛策略完成，并以23个步骤（最长的线性序列）进行。明显的合成特征包括一系列高度立体选择性底物控制的羟醛反应，以设定丙酸酯部分的甲基和羟基立体中心的特征性组装，对故意构象偏向的前体进行有效的非对映选择性Heck大环化以及后期通过无保护基团的前体的高产Stille偶联引入不稳定的侧链。一路走来，Z的改进，可靠协议醛的选择性Stork-Zhao-Wittig烯化反应得到发展，并设计了一种有效的方案，用于空间上受阻的特别是β-羟基酮的1，3- syn还原。在合成活动中，对这些不稳定的天然产物的固有异构化途径进行了更详细的了解。etnangiens的权宜之计和灵活的策略应该适合于设计这些RNA聚合酶抑制剂的类似物，从而能够进一步探索这些大环内酯类抗生素的有前途的生物潜力。
• An Efficient Procedure for the Direct Nucleophilic Substitution of the Abiko-Masamune Auxiliary
  作者：Dirk Menche、Jun Li、Pengfei Li

  DOI：10.1055/s-0029-1217819

  日期：2009.9

  An efficient method for the nucleophilic displace-ment of the Abiko-Masamune auxiliary is reported, which involves i-PrMgCl for intermediate ester activation.

  报告中介绍了一种亲核置换 Abiko-Masamune 助剂的有效方法，其中涉及 i-PrMgCl 进行中间酯活化。
• FUDZITA, EHJITI;NAGAO, JOSIMITSU;YAMADA, SEDZO
  作者：FUDZITA, EHJITI、NAGAO, JOSIMITSU、YAMADA, SEDZO

  DOI：——

  日期：——
• A novel catalytic asymmetric route towards skipped dienes with a methyl-substituted central stereogenic carbon
  作者：Yange Huang、Martín Fañanás-Mastral、Adriaan J. Minnaard、Ben L. Feringa

  DOI：10.1039/c3cc41021h

  日期：——

  A highly efficient method for the enantioselective synthesis of 1,4-dienes (skipped dienes) with a methyl-substituted central stereogenic carbon using copper-catalysed asymmetric allylic alkylation of diene bromides was developed. Excellent regio- and enantioselectivity (up to 97 : 3 SN2'/SN2 ratio and 99% ee) were achieved with broad substrate scope.

  开发了一种高效的方法，该方法通过铜催化的二烯溴化物的不对称烯丙基烷基化反应，用甲基取代的中心立体碳对映选择性合成1,4-二烯（跳过的二烯）。在广泛的底物范围内，可实现出色的区域选择性和对映体选择性（高达SN2'/ SN2比为97：3，ee为99％）。