(+)-(S)-4-hydroxy-β-ionone | 71629-15-7

• 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: (+)-(S)-4-hydroxy-β-ionone
• 英文别名: (E)-4-[(3S)-3-hydroxy-2,6,6-trimethylcyclohexen-1-yl]but-3-en-2-one
• CAS: 71629-15-7
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: LICNQDPDQQOXCU-FYJFLYSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(S)-4-hydroxy-β-ionone 在 4-二甲氨基吡啶 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 (9Z)-(4S)-4-<(tert-Butyldimethylsilyl)oxy>-β-ionylideneacetonitrile
  参考文献：
  名称：

  Retinoids and Related Compounds. Part 16. Synthesis of (+)-(4S)- and (-)-(4R)-(11Z)-4-Hydroxyretinals and Determination of the Absolute Stereochemistry of a Visual Pigment Chromophore in the Firefly Squid, Watasenia scintillans

  摘要：

  First syntheses of(+)-(4S)- and (-)-(4R)-(11Z)-4-hydroxyretinals (4-OH-RALs) (4a and 4b) were accomplished from (4S)- and (4R)-4-hydroxy-beta-ionones, respectively, to determine the absolute configuration of a visual pigment chromophore in Watasenia scintillans, which has been isolated as a new chromophore in the animal kingdom. The CD spectra of the native chromophore and its anti-oxime agreed with those of synthetic (4R)-compounds. Application of the CD exciton chirality method to the p-(dimethylamino)cinnamate of (4R)-4-OH-RAL also established the absolute configuration of the native chromophore as 4b.

  DOI：

  10.1021/jo00102a014
• 作为产物：
  描述：

  4-(3-hydroxy-2,6,6-trimethylcyclohex-1-enyl)but-3-en-2-one 在 吡啶 、 氢氧化钾 作用下， 以 甲醇 为溶剂， 生成 (+)-(S)-4-hydroxy-β-ionone
  参考文献：
  名称：

  （+）-（4 S）-和（-）-（4 R）-11 Z -4-羟基视黄醛的合成及视觉色素生色团在生物发光鱿鱼Watasenia scintillans中的绝对立体化学测定

  摘要：

  由（4S）-和（4R）-4-羟基-完成（+）-（4S）-和（-）-（4R）-11Z-4-羟基视黄醛（4-OH-RAL）1a和1b的合成。 β-紫罗兰酮分别用于确定Watasenia scintillans中视觉色素发色团的绝对构型。天然发色团及其抗肟的CD光谱与合成（4R）化合物的CD光谱一致。应用于（4R）-4-OH-RAL的对二甲基氨基肉桂酸酯的CD激子手性方法也将天然发色团的绝对构型确定为1b。

  DOI：

  10.1016/s0040-4039(00)75995-8

文献信息

• Synthese von (?)-(5R,6S)-5,6-Epoxy-5,6-dihydro-?-ionon
  作者：Murat Acemoglu、Walter Eschenmoser、Conrad Hans Eugster

  DOI：10.1002/hlca.19810640827

  日期：1981.12.16

  Synthesis of (−)-(5R,6S)-5,6-epoxy-5,6-dihydro-β-ionone

  （-）-（5 R，6 S）-5,6-环氧-5,6-二氢-β-紫罗兰酮的合成
• Synthese von (-)-(R)-4-Hydroxy-?-ionon und (-)-(5R, 6S)-5-Hydroxy-4,5-dihydro-?-ionon aus (-)-(S)-?-Ionon
  作者：Andreas Haag、Walter Eschenmoser、Conrad Hans Eugster

  DOI：10.1002/hlca.19800630103

  日期：1980.1.23

  Synthesis of (-)-(R)-4-Hydroxy-β-ionone and (-)-(5 R, 6 S)-5-Hydroxy-4,5-dihydro-α-ionone aus (-)-(S)-α-Ionone

  （-）-（R）-4-羟基-β-紫罗兰酮和（-）-（5 R，6 S）-5-羟基-4,5-二氢-α-紫罗兰酮的合成（-）-（S）-α-紫罗兰
• In Vitro Regio- and Stereoselective Oxidation of β-Ionone by Human Liver Microsomes
  作者：Shinsuke Marumoto、Ryoyu Shimizu、Genzoh Tanabe、Yoshiharu Okuno、Mitsuo Miyazawa

  DOI：10.1055/s-0042-112128

  日期：——

  The metabolism of the norisoprenoid β-ionone was investigated in vitro using human liver microsomes and 11 different recombinant cytochrome P450 enzymes expressed in Trichoplusia ni cells. β-Ionone was found to be oxidized via 4S-hydroxylation by CYP2B6 in human liver microsomes. CYP1A2 also regioselectively catalyzed the hydroxylation of β-ionone to yield 4-hydroxylation; this conversion was not stereoselective. Further kinetic analysis revealed that CYP2B6 exhibited the highest activity for β-ionone 4-hydroxylation. Kinetic analysis showed that K m and V max for oxidation of β-ionone by CYP1A2 and CYP2B6 was 107.9 ± 36.0 µM and 3200.3 ± 323.0 nmol/min/nmol P450 and 5.6 ± 1.2 µM and 572.8 ± 29.8 nmol/min/nmol P450, respectively. The reaction rates observed using human liver microsomes and recombinant CYP2B6 were very high compared with those of other CYP2B6 substrates reported thus far. These results suggest that β-ionone, a norisoprenoid present in nature, is one of the effective substrates for CYP2B enzymes in human liver microsomes. To the best of our knowledge, this is the first time that 4-hydroxy β-ionone has been described as a human metabolite of β-ionone.

  研究人员利用人体肝脏微粒体和在 Trichoplusia ni 细胞中表达的 11 种不同的重组细胞色素 P450 酶，在体外研究了去甲异戊烯δ-壬酮的代谢过程。研究发现，δ-壬酮在人肝脏微粒体中通过 4S- 羟基化作用被 CYP2B6 氧化。CYP1A2 也能区域选择性地催化δ-²-壬酮的羟基化反应，产生 4-羟基化反应；这种转化没有立体选择性。进一步的动力学分析表明，CYP2B6 在 β-ionone 4-hydroxylation 中表现出最高的活性。动力学分析表明，CYP1A2 和 CYP2B6 氧化δ-酮的 K m 和 V max 分别为 107.9 ± 36.0 µM 和 3200.3 ± 323.0 nmol/min/nmol P450，以及 5.6 ± 1.2 µM 和 572.8 ± 29.8 nmol/min/nmol P450。与迄今报道的其他 CYP2B6 底物相比，使用人肝微粒体和重组 CYP2B6 观察到的反应速率非常高。这些结果表明，δ-²-酮是一种存在于自然界中的去甲异肾上腺素类化合物，是人肝脏微粒体中 CYP2B 酶的有效底物之一。据我们所知，这是首次将 4-hydroxy β-ionone 描述为 β-ionone 的人类代谢物。
• Facile lipase catalysed syntheses of (S)-(+)-4-hydroxy-β-ionone and (S)-(+)-4-hydroxy-β-damascone: chiral flavorants and synthons
  作者：Gauri P. More、Sujata V. Bhat

  DOI：10.1016/j.tetlet.2013.05.089

  日期：2013.8

  Enantioselective syntheses of (S)-(+)-4-hydroxy-β-ionone and (S)-(+)-4-hydroxy-β-damascone have been achieved through pig pancreatic lipase catalysed trans-esterification. These molecules find utility as constituent in fruit-type fragrance and flavor formulations and as chiral synthons in asymmetric synthesis of bioactive terpenoids.

  （对映选择性合成小号（+） - - 4-羟基β紫罗兰酮和（）小号） - （+） - 4-羟基β大马酮已通过猪胰脂肪酶催化的实现反-esterification。这些分子在水果型香料和香精配方中用作成分，并在生物活性萜类化合物的不对称合成中用作手性合成子。
• Synthesis and plant growth inhibitory activities of (+)- and (−)-(2Z,4E)-5-(1′,2′-epoxy-2′,6′,6′-trimethylcyclohexyl)-3-methyl-2,4-pentadienoic acid☆
  作者：T ORITANI、K YAMASHITA

  DOI：10.1016/0031-9422(83)80010-7

  日期：——

  Abstract Chiral (+)- and (−)-enantiomers of (2Z,4E)-5-(1′,2′-epoxy-2′,6′,6′-trimethylcyclohexyl)-3-methyl-2,4-pentadienoic acid have been synthesized from the chiral epoxy alcohols (+)- and (−)-1′,2′-dihydro-1′,2′-epoxy-β-ionone, which were prepared by Katsuki-Sharpless' asymmetric epoxidation of β-cyclogeraniol. The (+)-enantiomer showed strong inhibitory activity in a rice seedling and lettuce germination

  摘要 (2Z,4E)-5-(1',2'-epoxy-2',6',6'-trimethylcyclohexyl)-3-methyl-2,4-的手性(+)-和(-)-对映异构体戊二烯酸是由手性环氧醇 (+)- 和 (-)-1',2'-dihydro-1',2'-epoxy-β-ionone 合成的，它们是通过 Katsuki-Sharpless 的不对称环氧化反应制备的β-环香叶醇。(+)-对映异构体在水稻幼苗和生菜发芽试验中显示出很强的抑制活性，而 (-)-对映异构体的活性低 103 倍。