(2E,4E,6E,8E)-3,6-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal | 165604-89-7

• 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: (2E,4E,6E,8E)-3,6-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
• CAS: 165604-89-7
• 化学式: C₂₀H₂₈O
• 分子量: 284.442
• InChiKey: SXPDOZRWVDYRMU-KMMFEFJCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  (2E,4E,6E,8E)-3,6-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal 、 2-[2-(6-Amino-2-tert-butoxycarbonylamino-hexanoylamino)-acetylamino]-3-(4-hydroxy-phenyl)-propionic acid methyl ester 在 potassium carbonate 作用下， 以 乙醇 为溶剂， 生成 2-(2-{2-tert-Butoxycarbonylamino-6-[(2E,4E,6E,8E)-3,6-dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraen-(E)-ylideneamino]-hexanoylamino}-acetylamino)-3-(4-hydroxy-phenyl)-propionic acid methyl ester
  参考文献：
  名称：

  含芳香族氨基酸的细菌视紫红质.Nε-Retinylidenelysyl肽的M412中间体的肽模型的光谱和MO研究

  摘要：

  为了研究周围微环境对细菌视紫红质发色团最大吸收的影响，制备了含有 Tyr 和 Phe 的 Ne-Retinylidenelysyl 肽。赖氨酰肽 Boc-Lys-Phe（或-Gly）-Tyr-OMe 的视黄叉基希夫碱的吸收最大值相对于缺乏 Tyr、Boc-Lys-Phe-Phe-OMe 和Boc-Lys-Phe-OMe。对含 Tyr 赖氨酰肽的 UV 和 13C NMR 研究证实了低介电介质中 Tyr 和视黄基部分之间的分子内相互作用。对某些 Tyr-Schiff 碱配合物模型的跃迁能和屏蔽常数的理论估计支持了具有 Tyr 侧链的 Schiff 碱的氢键形成。根据 1 H NMR 数据讨论了含 Tyr 的赖氨酰肽的侧链构象。Tyr 引起的氢键位移估计不小于 10 nm。

  DOI：

  10.1246/bcsj.59.2157
• 作为产物：
  描述：

  (E,E)-(5-hydroxy-3-methylpenta-1,3-dienyl)boronic acid 在 manganese(IV) oxide 、 四(三苯基膦)钯 、 正丁基锂 、 氢氧化铊(Ⅰ) 、 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 (2E,4E,6E,8E)-3,6-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
  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

文献信息

• Experimental and Theoretical Analysis of the Steric Tolerance of the Binding Site of Bacterioopsin with the Use of Side-Chain Methyl-Shifted Retinal Analogs
  作者：Angel R. de Lera、Beatriz Iglesias、Jesus Rodriguez、Rosana Alvarez、Susana Lopez、Xavier Villanueva、Esteve Padros

  DOI：10.1021/ja00136a021

  日期：1995.8

  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.
• Spectroscopic and MO Study of Peptide Models for the M₄₁₂Intermediate of Bacteriorhodopsin.<i>N</i>^ε-Retinylidenelysyl Peptides Containing Aromatic Amino Acids
  作者：Minoru Sakurai、Satoshi Tomomasa、Yûji Seiya、Yoshio Inoue、Riichirô Chûjô

  DOI：10.1246/bcsj.59.2157

  日期：1986.7

  Ne-Retinylidenelysyl peptides containing Tyr and Phe were prepared in order to investigate the effect of the surrounding microenvironment on the absorption maximum of the chromophore of bacteriorhodopsin. The absorption maximum of the retinylidene Schiff base of the lysyl peptide, Boc–Lys–Phe(or –Gly)–Tyr–OMe, was shifted to the red relative to the peptides lacking Tyr, Boc–Lys–Phe–Phe–OMe and Boc–Lys–Phe–OMe

  为了研究周围微环境对细菌视紫红质发色团最大吸收的影响，制备了含有 Tyr 和 Phe 的 Ne-Retinylidenelysyl 肽。赖氨酰肽 Boc-Lys-Phe（或-Gly）-Tyr-OMe 的视黄叉基希夫碱的吸收最大值相对于缺乏 Tyr、Boc-Lys-Phe-Phe-OMe 和Boc-Lys-Phe-OMe。对含 Tyr 赖氨酰肽的 UV 和 13C NMR 研究证实了低介电介质中 Tyr 和视黄基部分之间的分子内相互作用。对某些 Tyr-Schiff 碱配合物模型的跃迁能和屏蔽常数的理论估计支持了具有 Tyr 侧链的 Schiff 碱的氢键形成。根据 1 H NMR 数据讨论了含 Tyr 的赖氨酰肽的侧链构象。Tyr 引起的氢键位移估计不小于 10 nm。