lutein | 31272-50-1

• 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: lutein
• 英文别名: meso-zeaxanthin；(3R,3'S)-zeaxanthin；(3R,3'S)-β,β-carotene-3,3'-diol；(1R)-4-[(1E,3E,5E,7E,9E,11E,13E,15E,17E)-18-[(4S)-4-hydroxy-2,6,6-trimethylcyclohexen-1-yl]-3,7,12,16-tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaenyl]-3,5,5-trimethylcyclohex-3-en-1-ol
• CAS: 31272-50-1
• 化学式: C₄₀H₅₆O₂
• 分子量: 568.883
• InChiKey: JKQXZKUSFCKOGQ-YOPUJPICSA-N

物化性质

• 熔点：
  207.5-208 °C
• 沸点：
  711.4±55.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.9
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  lutein 在 碘 、 sodium metabisulfite 、 sodium bromate 、 碳酸氢钠 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.5h， 以72%的产率得到3,3'-二羟基-beta,beta-胡罗卜素-4,4'-二酮
  参考文献：
  名称：

  (3R,3'S)-玉米黄质从(3R,3'R,6'R)-叶黄素和叶黄素酯部分合成纯(3R,3'S)-虾青素的简单高效方法及其形成机制的理论研究

  摘要：

  类胡萝卜素是天然化合物，对促进和维持人类健康具有重要作用。合成虾青素是水产养殖业要求很高的产品，但天然虾青素则不然。人们已经开发出多种策略来合成这种类胡萝卜素。尽管如此，这些方法不仅提供了有限的全球产量，而且其主要商业来源也给人类带来了一些健康风险。在此贡献中，(3R,3'R,6'R)-叶黄素 (1) 酯的一锅碱催化反应成功实现了异构化过程，可轻松获得高达 95% 的内消旋玉米黄质 (2) ，进而被氧化为 (3R,3'S)-虾青素 (3)，总产率为 68%。使用 UV 照射（365 nm）进行 5 分钟的相同氧化提供了最高的总体产率（76%）。这些化学转化还显着降低了与人类潜在消费相关的健康风险。此外，这是第一次仅半合成获得一种构型异构体。我们还使用密度泛函理论 (DFT) 计算研究了人们对这两种化合物的形成机制知之甚少的情况。这些理论研究表明，异构化涉及 C-6' 处的碱催化去质子化，然后是

  DOI：

  10.3390/molecules24071386
• 作为产物：
  描述：

  叶黄素 在 isomerohydrolase 作用下， 反应 48.0h， 生成 lutein
  参考文献：
  名称：

  RPE65在脊椎动物眼中还具有作为中玉米黄质异构酶的叶黄素的功能。

  摘要：

  类胡萝卜素是脊椎动物无法从头合成的植物来源的色素分子，可以保护灵长类视网膜的中央凹免受氧化应激和光损伤。中观玉米黄质是一种特定于眼的类胡萝卜素，没有常见的饮食来源。它是存在于中央凹中心的三种主要类胡萝卜素之一，但在眼中产生该类胡萝卜素的机制尚不清楚。异构酶被认为是通过双键移位机制将叶黄素转化为内消旋玉米黄质的原因，但其身份难以捉摸。我们以前发现中观玉米黄质在光照下在鸡胚视网膜色素上皮（RPE）/脉络膜中以发育受调控的方式产生。在本研究中，我们表明RPE65是脊椎动物视觉周期的异构酶，它催化全反式视黄醇酯异构化为11-顺式-视黄醇，也是在体内产生内消旋-玉米黄质的异构酶。脊椎动物。在当时它的RNA上调23倍观-zeaxanthin生产鸡眼睛的发育过程中，我们目前的证据表明，在细胞培养或者导致鸡或人RPE65的过度生产的观叶黄素中的玉米黄素。RPE65功能的药理学抑制导致的显著抑制观鸡眼睛发育

  DOI：

  10.1073/pnas.1706332114

文献信息

• Process for Synthesis of (3S)- and (3R)-3-Hydroxy-Beta-Ionone, and Their Transformation to Zeaxanthin and Beta-Cryptoxanthin
  申请人：Khachik Frederick

  公开号：US20090311761A1

  公开（公告）日：2009-12-17

  (3R)-3-Hydroxy-β-ionone and (3S)-3-hydroxy-β-ionone are two important intermediates in the synthesis of carotenoids with β-end group such as lutein, zeaxanthin, β-cryptoxanthin, and their stereoisomers. Among the various stereoisomers of these carotenoids, only (3R,3′R,6′R)-lutein, (3R,3′R)-zeaxanthin, and (3R)-β-cryptoxanthin are present in commonly consumed fruits and vegetables. There are 3 possible stereoisomers for zeaxanthin, these are: dietary (3R,3′R)-zeaxanthin (1), non-dietary (3S,3′S)-zeaxanthin (2), and non-dietary (3R,3′S;meso)-zeaxanthin (3) which is a presumed metabolite of dietary lutein. Dietary lutein as well as 1 and 3 are accumulated in the human macula and have been implicated in the prevention of age-related macular degeneration. (3R)-β-Cryptoxanthin (4) is also present in selected ocular tissues at a very low concentration whereas its enantiomer (3S)-β-cryptoxanthin (5) is absent in foods and human plasma. The present invention relates to a process for the synthesis of (3R)-3-hydroxy-β-ionone and its (3S)-enantiomer in high optical purity from commercially available (rac)-α-ionone. The key intermediate for the synthesis of these hydroxyionones is 3-keto-α-ionone ketal that was prepared from (rac)-α-ionone after protection of this ketone as a 1,3-dioxolane. Reduction of 3-keto-α-ionone ketal followed by deprotection, lead to 3-hydroxy-α-ionone that was transformed into (rac)-3-hydroxy-β-ionone by base-catalyzed double bond isomerization in 46% overall yield from (rac)-α-ionone. The racemic mixture of these hydroxyionones was then resolved by enzyme-mediated acylation in 96% ee. (3R)-3-Hydroxy-β-ionone and its (3S)-enantiomer were respectively transformed to (3R)-3-hydroxy-(β-ionylideneethyl)triphenylphosphonium chloride [(3R)—C 15 -Wittig salt] and its (3S)-enantiomer [(3S)—C 15 -Wittig salt] according to known procedures. Double Wittig condensation of these Wittig salts with commercially available 2,5-dimethylocta-2,4,6-triene-1,8-dial provided all 3 stereoisomers of zeaxanthin (1-3). Similarly, (3R)—C 15 -Wittig and its (3S)-enantiomer were each coupled with β-apo-12′-carotenal to yield 4 and 5.

  (3R)-3-羟基-β-离子酮和(3S)-3-羟基-β-离子酮是合成带有β末端基团的类胡萝卜素如叶黄素、玉米黄质、β-隐黄素及其立体异构体的两个重要中间体。在这些类胡萝卜素的各种立体异构体中，只有(3R,3′R,6′R)-叶黄素、(3R,3′R)-玉米黄质和(3R)-β-隐黄素存在于常见的水果和蔬菜中。玉米黄质有3种可能的立体异构体，分别是：膳食(3R,3′R)-玉米黄质（1）、非膳食(3S,3′S)-玉米黄质（2）和非膳食(3R,3′S;meso)-玉米黄质（3），后者被认为是膳食叶黄素的代谢产物。膳食叶黄素以及1和3在人类黄斑中积累，并被认为有助于预防年龄相关性黄斑变性。 (3R)-β-隐黄素（4）也以极低浓度存在于选定的眼部组织中，而其对映异构体(3S)-β-隐黄素（5）在食物和人类血浆中不存在。本发明涉及一种从市售的（rac）-α-离子酮合成（3R）-3-羟基-β-离子酮及其（3S）对映体的高光学纯度的过程。合成这些羟基酮的关键中间体是从（rac）-α-离子酮制备的3-酮-α-离子酮缩酮，在保护该酮为1,3-二氧兰后得到。随后对3-酮-α-离子酮缩酮进行还原和去保护，得到3-羟基-α-离子酮，再经碱催化的双键异构化，从（rac）-α-离子酮中总产率为46%地转化为（rac）-3-羟基-β-离子酮。然后通过酶介导的酰化将这些羟基酮的外消旋混合物在96%纯度下分离。 (3R)-3-羟基-β-离子酮及其（3S）对映体分别按照已知程序转化为(3R)-3-羟基-(β-离子乙基)三苯基膦盐[(3R)—C15-Wittig盐]和其（3S）对映体[(3S)—C15-Wittig盐]。这些Wittig盐与市售的2,5-二甲基辛-2,4,6-三烯-1,8-二醛进行双Wittig缩合，提供了叶黄素的3种立体异构体（1-3）。类似地，(3R)—C15-Wittig及其（3S）对映体分别与β-脱氧-12'-类胡萝卜醛偶联，得到4和5。
• Process or synthesis of (3S)- and (3R)-3-hydroxy-beta-ionone, and their transformation to zeaxanthin and beta-cryptoxanthin
  申请人：University of Maryland, College Park

  公开号：US08222458B2

  公开（公告）日：2012-07-17

  Disclosed is a process for the synthesis of (3R)-3-hydroxy-β-ionone and its (3S)-enantiomer in high optical purity from commercially available (rac)-α-ionone. The key intermediate for the synthesis of these hydroxyionones is 3-keto-α-ionone ketal that was prepared from (rac)-α-ionone after protection of this ketone as a 1,3-dioxolane. Reduction of 3-keto-α-ionone ketal followed by deprotection, lead to 3-hydroxy-α-ionone that was transformed into (rac)-3-hydrox-β-ionone by base-catalyzed double bond isomerization in 46% overall yield from (rac)-α-ionone. The racemic mixture of these hydroxyionones was then resolved by enzyme-mediated acylation in 96% ee. (3R)-3-Hydroxy-β-ionone and its (3S)-enantiomer were respectively transformed to (3R)-3-hydroxy-(β-ionylideneethyl)triphenylphosphonium chloride [(3R)-C15-Wittig salt] and its (3S)-enantiomer [(3S)-C15-Wittig salt] according to known procedures. Double Wittig condensation of these Wittig salts with commercial available 2,5- dimethtylocta-2,4,6-triene-1,8-dial provided all 3 stereoisomers of zeaxanthin. Similarly, (3R)-C15-Wittig and its (3S)-enantiomer were each coupled with β-apo-12′-carotenal.

  本文披露了一种从商业可获得的（rac）-α-离子酮合成（3R）-3-羟基-β-离子酮及其（3S）对映体的高光学纯度的过程。合成这些羟基离子酮的关键中间体是从（rac）-α-离子酮制备的3-酮-α-离子酮缩酮，经过将该酮保护为1,3-二氧杂环后得到。还原3-酮-α-离子酮缩酮，然后去保护，得到3-羟基-α-离子酮，通过碱催化的双键异构化，从（rac）-α-离子酮中总产率为46%转化为（rac）-3-羟基-β-离子酮。这些羟基离子酮的混合物随后通过酶介导的酰化在96%的ee下分离。（3R）-3-羟基-β-离子酮及其（3S）对映体分别按照已知程序转化为（3R）-3-羟基-(β-离子基乙基)三苯基膦盐[(3R)-C15-Wittig盐]和其（3S）对映体[(3S)-C15-Wittig盐]。将这些Wittig盐与商业可获得的2,5-二甲基辛二烯-1,8-二醛进行双Wittig缩合，得到所有3种类脂黄素的立体异构体。类似地，（3R）-C15-Wittig及其（3S）对映体分别与β-脱氧-12'-类胡萝卜素醛偶联。
• Synthese von optisch aktiven, natürlichen Carotinoiden und strukturell verwandten Naturprodukten. V. Synthese von (3R, 3′R)-, (3S, 3′S)- und (3R,3′S; meso)-Zeaxanthin durch asymmetrische Hydroborierung. Ein neuer Zugang zu Optisch aktiven Carotinoidbauste
  作者：August Rüttimann、Hans Mayer

  DOI：10.1002/hlca.19800630615

  日期：1980.9.17

  Synthesis of Optically Active Natural Carotenoids and Structurally Related Compounds. V. Synthesis of (3R, 3′R)-, (3S, 3′S)- and (3R,3′S; meso)-zeaxanthin by Asymmetric Hydroboration. A New Approach to Optically Active Carotenoid Building Units

  光学活性天然类胡萝卜素和结构相关化合物的合成。V.（3合成[R '，3 - [R - （，3）小号，3'小号-和（3）- [R，3' š ;内消旋通过不对称硼氢化-zeaxanthin）。光学活性类胡萝卜素构建单元的新方法
• Novel xanthophyll composition containing trans, meso-zeaxanthin, trans, R, R-zeaxanthin and trans, R, R-lutein useful for nutrition and health care and a process for its preparation
  申请人：Kumar T.K. Sunil

  公开号：US20070265351A1

  公开（公告）日：2007-11-15

  The present invention relates to xanthophyll composition containing (trans, meso)-zeaxanthin), (trans, R,R)-zeaxanthin and (trans, R,R)-lutein useful for nutrition and health care and a process for its preparation. More particularly, the invention relates to a xanthophylls composition containing at least 80% by weight of total xanthophylls, out of which the (trans,3R,3′S, meso)-zeaxanthin content is at least 80%, the remaining being (trans, R,R)-zeaxanthin, (trans, R,R)-lutein and trace amounts of other carotenoids. This invention further provides a xanthophyll composition containing at least 80% by weight of total xanthophylls, out of which at least 50% being (trans, R,R)-zeaxanthin, the remaining being (trans,3R,3′S, meso)-zeaxanthin, (trans, R,R)-lutein and trace amounts of other carotenoids.

  本发明涉及一种含有（反式，间位异构体）玉米黄素（zeaxanthin）、（反式，R,R）-玉米黄素和（反式，R,R）-叶黄素的黄色素组合物，用于营养和保健，以及其制备方法。更具体地，该发明涉及一种黄色素组合物，其含有至少80%的总黄色素重量，其中（反式，3R,3′S，间位异构体）玉米黄素含量至少为80%，其余部分为（反式，R,R）-玉米黄素、（反式，R,R）-叶黄素和微量其他类胡萝卜素。本发明进一步提供一种黄色素组合物，其含有至少80%的总黄色素重量，其中至少50%为（反式，R,R）-玉米黄素，其余部分为（反式，3R,3′S，间位异构体）玉米黄素、（反式，R,R）-叶黄素和微量其他类胡萝卜素。
• [EN] NOVEL XANTHOPHYLL COMPOSITION CONTANING (TRANS, MESO) - ZEAXANTHIN, AND A PROCESS FOR ITS PREPARATION<br/>[FR] NOUVELLE COMPOSITION À BASE DE XANTHOPHYLLES CONTENANT DE LA (TRANS, MÉSO)-ZÉAXANTHINE, ET SON PROCÉDÉ DE PRÉPARATION
  申请人：OMNIACTIVE HEALTH TECHNOLOGIES

  公开号：WO2009019712A1

  公开（公告）日：2009-02-12

  The invention disclosed in this application relates to a novel xanthophylls composition containing trans-isomeric forms of meso-zeaxanthin, zeaxanthin and lutein useful for nutrition and health care and a process for its preparation are disclosed. The process involves heating a mixture of lutein containing material along with an aromatic alcohol and alkali hydride followed by purification.

  本申请揭示的发明涉及一种新型黄质组合物，其中包含对营养和保健有用的反异构形式的中间-玉米黄质、玉米黄质和叶黄素，并公开了其制备方法。该方法涉及加热含有叶黄素材料的混合物，以及芳香醇和碱性氢化物，然后进行纯化。