all-trans-11-methylretinal | 194715-64-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: all-trans-11-methylretinal
• 英文别名: (2E,4E,6E,8E)-3,5,7-trimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
• CAS: 194715-64-5
• 化学式: C₂₁H₃₀O
• 分子量: 298.469
• InChiKey: RRNMAWQHIDHHNP-YPTHUKSOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  all-trans-11-methylretinal 在 aporetinochrome 作用下， 生成 (11Z)-11-methylretinal
  参考文献：
  名称：

  Contribution of Methyls in Retinal Side Chain to Regioselective Photoisomerization of Retinochromes

  摘要：

  合成了全反式-9-去甲基-11-甲基视黄醛，以阐明视黄醛色素中的疏水部分与视黄醛的 9-甲基取代基之间的色素相互作用。对其色素进行光照射可有效地得到 11-顺式异构体，其区域选择性为 90%，而对 9-去甲基视黄醛进行光照射可得到 11-顺式异构体，其区域选择性为 49%。与其他视黄红类似物相比，9-或 11-甲基取代基是高区域选择性光异构化的必要条件，而 13-甲基则不是。

  DOI：

  10.1246/cl.1999.1051
• 作为产物：
  描述：

  (7E,9E)-beta-离子亚基乙醛 在 1,2-环氧丁烷 、 碘 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醇 、 Petroleum ether 为溶剂， 反应 136.5h， 生成 all-trans-11-methylretinal
  参考文献：
  名称：

  Efficient preparation of 9-Z-11-methylretinal and 11-Z-11-methylretinal

  摘要：

  [2-(beta-Ionylidene)propyl]triphenylphosphonium bromide is reacted with 3-methyl-4-oxobut-2-enenitrile in refluxing 1,2-epoxybutane to give a mixture of 11-Z- and all-E-11-methylretinal via DIBAL-H reduction. In an analogous fashion, beta-ionyl triphenylphosphonium bromide is reacted with 3,5-dimethyl-6-oxohexa-2,4-dienenitrile in 1,2-epoxybutane followed by subsequent DIBAL-H reduction to afford a mixture of new products consisting of 9-Z-11-methylretinal, its all-E isomer and 1-(2',6',6'-trimethylcyclohex-2'-en-1'-yl)-6-(buten-2 ''-al-3 ''-yl)-3,5-dimethylcyclohexa-1,3-diene. These molecules were obtained in pure form by HPLC. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.11.144

文献信息

• Synthesis of C11-to-C14 methyl-shifted all-<i>trans</i>-retinal analogues and their activities on human aldo-keto reductases
  作者：Aurea Rivas、Raquel Pequerul、Vito Barracco、Marta Domínguez、Susana López、Rafael Jiménez、Xavier Parés、Rosana Alvarez、Jaume Farrés、Angel R. de Lera

  DOI：10.1039/d0ob01084g

  日期：——

  The synthesis of these retinoids was based on the formation of a C10–C11 single bond of the pentaene skeleton starting from a trienyl iodide and the corresponding dienylstannanes and dienylsilanes, using the Stille–Kosugi–Migita and Hiyama–Denmark cross-coupling reactions, respectively. Since these reagents differ by the location and presence of methyl groups at the dienylorganometallic fragment, the

  人醛基酮还原酶（AKR）是参与将所有反式-视网膜还原为全反式-视黄醇（维生素A）的酶，因此有助于控制生物体中类维生素A的水平。一系列C11-C14甲基转移（相对于天然C13-甲基）全反式的构效关系研究已经报道了-视网膜类似物作为AKR的假定底物。这些类维生素A的合成基于戊烯骨架的C10–C11单键的形成，分别从Stille–Kosugi–Migita和Hiyama–Denmark交叉偶联反应开始，从三苯基碘化物以及相应的二苯基锡烷和二苯基硅烷开始。 。由于这些试剂的不同之处在于二烯基有机金属片段上甲基的位置和存在，因此该研究还提供了对不同位置异构体进行交叉偶联的能力以及这些过程对位阻的敏感性的见解。所得的C11至C14甲基转移的全反式尽管已注意到底物特异性的相关差异，但在用AKR1B1和AKR1B10酶进行测试时，发现视网膜类似物是活性底物。对于AKR1B1，所有类似物均比母体全反式视网膜表现出更高的催化效率（k
• Unusual Conformation and Photoisomerization of Retinochrome Analogues with 11-Methylretinals
  作者：Kazuo Tsujimoto、Yasuhiro Shirasaka、Taku Mizukami、Mamoru Ohashi

  DOI：10.1246/cl.1997.813

  日期：1997.8

  NOESY measurement. The formed retinochrome-analogues with 11-Me-, 11-Me-13-deMe- and 11-Me-9,13-dideMe-retinals showed their absorption maxima at 450, 470 and 470 nm, respectively. The enzymatic photoisomerization of their retinochrome-analogues gave the 11-cis isomers in 90-91 % regioselectivity. The CD spectra of 11-methylretinochrome exhibited the intense β-band with extremely weak α-band.

  合成了三种 11-甲基视黄醛，以阐明甲基取代对视黄色素类似物形成及其性质的影响。基于 NOESY 测量发现 11-甲基视黄醛的稳定构象为 6,10,12-tri-S-cis 构象。形成的具有 11-Me-、11-Me-13-deMe-和 11-Me-9,13-dideMe-视黄醛的视黄色素类似物分别在 450、470 和 470 nm 处显示出它们的吸收最大值。它们的视黄色素类似物的酶促光异构化产生了 90-91% 区域选择性的 11-顺式异构体。11-甲基视黄色素的CD光谱表现出强烈的β-带和极弱的α-带。
• Contribution of Methyls in Retinal Side Chain to Regioselective Photoisomerization of Retinochromes
  作者：Kazuo Tsujimoto、Jun’ichirou Sugiura、Nobuaki Takemori、Taku Mizukami

  DOI：10.1246/cl.1999.1051

  日期：1999.10

  All-trans-9-demethyl-11-methylretinal was synthesized to elucidate the chromophoric interaction between hydrophobic part in retinochrome and 9-methyl substituent of retinal. Photoirradiation of its pigment efficiently gave the 11-cis-isomer in 90% regioselectivity, whereas that of 9-demethylretinochrome provided the 11-cis isomer in 49% selectivity. Structural contribution to regiospecific photoisomerization was proved, in comparison with the other retinochrome analogues, that 9- or 11-methyl substituent is a requisite for highly regioselective photoisomerization, but 13-methyl group is not.

  合成了全反式-9-去甲基-11-甲基视黄醛，以阐明视黄醛色素中的疏水部分与视黄醛的 9-甲基取代基之间的色素相互作用。对其色素进行光照射可有效地得到 11-顺式异构体，其区域选择性为 90%，而对 9-去甲基视黄醛进行光照射可得到 11-顺式异构体，其区域选择性为 49%。与其他视黄红类似物相比，9-或 11-甲基取代基是高区域选择性光异构化的必要条件，而 13-甲基则不是。
• Efficient preparation of 9-Z-11-methylretinal and 11-Z-11-methylretinal
  作者：Prativa B.S. Dawadi、Michiel A. Verhoeven、Johan Lugtenburg

  DOI：10.1016/j.tetlet.2010.11.144

  日期：2011.2

  [2-(beta-Ionylidene)propyl]triphenylphosphonium bromide is reacted with 3-methyl-4-oxobut-2-enenitrile in refluxing 1,2-epoxybutane to give a mixture of 11-Z- and all-E-11-methylretinal via DIBAL-H reduction. In an analogous fashion, beta-ionyl triphenylphosphonium bromide is reacted with 3,5-dimethyl-6-oxohexa-2,4-dienenitrile in 1,2-epoxybutane followed by subsequent DIBAL-H reduction to afford a mixture of new products consisting of 9-Z-11-methylretinal, its all-E isomer and 1-(2',6',6'-trimethylcyclohex-2'-en-1'-yl)-6-(buten-2 ''-al-3 ''-yl)-3,5-dimethylcyclohexa-1,3-diene. These molecules were obtained in pure form by HPLC. (C) 2010 Elsevier Ltd. All rights reserved.