(4R)-4-hydroxy-2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde | 42926-75-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R)-4-hydroxy-2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde
• 英文别名: (4R)-4-hydroxy-2,6,6-trimethylcyclohex-1-enecarbaldehyde；Hydroxy-beta-cyclocitral；(4R)-4-hydroxy-2,6,6-trimethylcyclohexene-1-carbaldehyde
• CAS: 42926-75-0
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: SWPMTVXRLXPNDP-MRVPVSSYSA-N

物化性质

• 沸点：
  267.2±40.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (4R)-4-hydroxy-2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde 在 sodium methylate 、 间氯过氧苯甲酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (3S,5R,6S,7E)-5,6-epoxy-3-hydroxy-7-megastigmen-9-one
  参考文献：
  名称：

  Measurement of xanthoxin in higher plant tissues using 13c labelled internal standards

  摘要：

  DOI：

  10.1016/0031-9422(90)85398-y
• 作为产物：
  描述：

  1-hydroxymethyl-2,6,6-trimethylcyclohexa-1,3-diene 在 sodium acetate 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 10.0h， 生成 (4R)-4-hydroxy-2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde
  参考文献：
  名称：

  合成胡萝卜素，天然胡萝卜素和天然维生素。V.合成冯（3 - [R，3' - [R ）- ，（3小号，3'小号） - UND（3 - [R，3'小号;内消旋）-Zeaxanthin第三人以asymmetrische Hydroborierung。Ein neuer Zugang zu Optisch aktiven Carotinoidbausteinen。VorläufigeMitteilung †

  摘要：

  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

  DOI：

  10.1002/hlca.19800630615

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。
• 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
• Oxidative Remodeling of Chromoplast Carotenoids
  作者：Florence Bouvier、Claude Suire、Jérôme Mutterer、Bilal Camara

  DOI：10.1105/tpc.006536

  日期：2003.1

  The accumulation of three major carotenoid derivatives—crocetin glycosides, picrocrocin, and safranal—is in large part responsible for the color, bitter taste, and aroma of saffron, which is obtained from the dried styles of Crocus. We have identified and functionally characterized the Crocus zeaxanthin 7,8(7′,8′)-cleavage dioxygenase gene (CsZCD), which codes for a chromoplast enzyme that initiates the biogenesis of these derivatives. The Crocus carotenoid 9,10(9′,10′)-cleavage dioxygenase gene (CsCCD) also has been cloned, and the comparison of substrate specificities between these two enzymes has shown that the CsCCD enzyme acts on a broader range of precursors. CsZCD expression is restricted to the style branch tissues and is enhanced under dehydration stress, whereas CsCCD is expressed constitutively in flower and leaf tissues irrespective of dehydration stress. Electron microscopy revealed that the accumulation of saffron metabolites is accompanied by the differentiation of amyloplasts and chromoplasts and by interactions between chromoplasts and the vacuole. Our data suggest that a stepwise sequence exists that involves the oxidative cleavage of zeaxanthin in chromoplasts followed by the sequestration of modified water-soluble derivatives into the central vacuole.

  藏红花的颜色、苦味和香气在很大程度上是由三种主要类胡萝卜素衍生物--藏红花黄素苷、苦味素和黄花醛--的积累造成的，藏红花是从藏红花的干燥花柱中提取的。我们发现了番红花玉米黄质 7,8（7′,8′）-裂解二氧酶基因（CsZCD），并对其进行了功能鉴定，该基因编码的染色体酶启动了这些衍生物的生物生成。此外，还克隆了番红花类胡萝卜素 9,10（9′,10′）-裂解二加氧酶基因（CsCCD），对这两种酶的底物特异性进行比较后发现，CsCCD 酶作用于更广泛的前体。CsZCD 的表达仅限于花柱分枝组织，在脱水胁迫下会增强，而 CsCCD 则在花和叶组织中组成型表达，与脱水胁迫无关。电子显微镜显示，藏红花代谢物的积累伴随着淀粉体和染色质的分化以及染色质和液泡之间的相互作用。我们的数据表明，存在着一个循序渐进的过程，包括在色质体中氧化裂解玉米黄质，然后将经过修饰的水溶性衍生物螯合到中心液泡中。
• Novel carotenoid cleavage dioxygenase catalyzes the first dedicated step in saffron crocin biosynthesis
  作者：Sarah Frusciante、Gianfranco Diretto、Mark Bruno、Paola Ferrante、Marco Pietrella、Alfonso Prado-Cabrero、Angela Rubio-Moraga、Peter Beyer、Lourdes Gomez-Gomez、Salim Al-Babili、Giovanni Giuliano

  DOI：10.1073/pnas.1404629111

  日期：2014.8.19

  Saffron is a triploid, sterile species whose red stigmas constitute the most expensive spice on Earth. The color, the taste, and the aroma of the spice are owed to the crocus-specific apocarotenoid accumulation of crocetin/crocins, picrocrocin, and safranal. Through deep transcriptome analysis, we identified a novel carotenoid cleavage dioxygenase (CCD) whose expression profile parallels the production of crocetin. Using in bacterio , in vitro, and in planta functional assays, we demonstrate that CCD2 is the dioxygenase catalyzing the first dedicated step in saffron crocetin biosynthesis starting from the carotenoid zeaxanthin.

  番红花是一种三倍体、不育的物种，其红色柱头构成了地球上最昂贵的香料。该香料的颜色、味道和香气归功于番红花特有的类胡萝卜素代谢产物积累，包括藏红花素/藏红花苷、苦藏红花素和番红花醛。通过深入的转录组分析，我们鉴定出一种新的类胡萝卜素裂解双氧酶（CCD），其表达谱与藏红花素的产生相似。通过in bacterio、in vitro和in planta功能分析，我们证明CCD2是催化从类胡萝卜素玉米黄质开始的藏红花素生物合成的第一个专门步骤的双氧酶。

• METHODS AND MATERIALS FOR RECOMBINANT PRODUCTION OF SAFFRON COMPOUNDS
  申请人：Evolva SA

  公开号：EP2742131B1

  公开（公告）日：2018-11-28