(E,E)-(5-hydroxy-4-methylpenta-1,3-dien-1-yl)boronic acid | 165604-91-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: (E,E)-(5-hydroxy-4-methylpenta-1,3-dien-1-yl)boronic acid
• 英文别名: [(E,E)-(5-hydroxy-4-methylpent-1,3-dien-4-yl)]boronic acid；((1E,3E)-5-Hydroxy-4-methylpenta-1,3-dien-1-yl)boronic acid；[(1E,3E)-5-hydroxy-4-methylpenta-1,3-dienyl]boronic acid
• CAS: 165604-91-1
• 化学式: C₆H₁₁BO₃
• 分子量: 141.963
• InChiKey: QXGSBRCWEARTGC-PIXFVPMGSA-N

物化性质

• 沸点：
  337.0±44.0 °C(Predicted)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.51
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E,E)-(5-hydroxy-4-methylpenta-1,3-dien-1-yl)boronic acid 在 manganese(IV) oxide 、 四(三苯基膦)钯 、 氢氧化铊(Ⅰ) 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 17.0h， 生成 all-trans-13-demethyl-14-methylretinal
  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：

  (E)-2-methylpent-2-en-4-yn-1-ol 、 儿萘酚硼烷 以52%的产率得到(E,E)-(5-hydroxy-4-methylpenta-1,3-dien-1-yl)boronic acid
  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

• Stereocontrolled synthesis of retinoids functionalized at C-13 by suzuki coupling reactions
  作者：Rosana Alvarez、Beatriz Iglesias、Angel R. de Lera

  DOI：10.1016/s0040-4020(99)00861-3

  日期：1999.11

  The retinal analogues (13Z)-13-bromo-13-desmethylretinal (3) and (13E)-20,20,20-trifluororetinal (4) have been efficiently synthesized using the palladium-catalyzed cross-coupling of boronic acid 8 and electrophiles 9 and 10, respectively. For the first analogue, the coupling of 8 and the gem-dibromide 9 took place with high stereoselectivity. The configuration of the C13-C14 double bond in 4 relied

  视网膜类似物（13Z）-13-溴-13- desmethylretinal（3）和（13 Ë）-20,20,20-trifluororetinal（4），使用已被有效地合成的钯催化的硼酸的交叉偶联8和亲电试剂9和10。对于第一个类似物，8和gem -dibromide 9的偶联具有很高的立体选择性。C13-C14双键在4中的构型取决于立体选择性制备和β-酮酸酯15的三氟甲磺酸Z - 10的偶联。