(4R*,6R*)-2,2,6-Trimethyl-4-hydroxycyclohexan-1-one | 60046-50-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R*,6R*)-2,2,6-Trimethyl-4-hydroxycyclohexan-1-one
• 英文别名: trans-4-hydroxy-2,2,6-trimethylcyclohexanone；Actinol；(4R,6R)-4-hydroxy-2,2,6-trimethylcyclohexan-1-one
• CAS: 60046-50-6
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: CSPVUHYZUZZRGF-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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*,6R*)-2,2,6-Trimethyl-4-hydroxycyclohexan-1-one 在 hydroxy(triphenyl)silane,oxovanadium 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 sodium tetrahydroborate 、 水 、 三乙胺 、 苯甲酸 作用下， 以 xylene 为溶剂， 生成 3-[(4R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethylcyclohex-1-enyl]propan-1-ol
  参考文献：
  名称：

  First total synthesis of crassostreaxanthin B

  摘要：

  首次全面合成crassostreaxanthin B 1是通过使用路易斯酸对环氧化物3a,b进行立体选择性重排所制备的四取代烯烃化合物5完成的。

  DOI：

  10.1039/a901116a
• 作为产物：
  描述：

  (6R)-2,2,6-三甲基-1,4-环己烷二酮 在 Raney-Ni (W₂-activity) 氢气 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以83%的产率得到(4R*,6R*)-2,2,6-Trimethyl-4-hydroxycyclohexan-1-one
  参考文献：
  名称：

  （+）-和（-）-boscialin及其1'-表象素的总合成和生物活性。

  摘要：

  天然（-）-boscialin [（-）-1]最近被描述为各种药用植物的成分之一。为了获得更多用于研究其生物学活性的材料，我们进行了（-）-1及其异构体的合成。从手性结构单元2开始，合成的关键步骤涉及区域选择性还原和亲核加成。天然产物（+）-波西林霉素[（+）-1]的对映异构体可以通过酸催化将羟基酮4异构化为（+）-3而得到。以（-）-3开始合成会生成具有天然绝对构型的（-）-boscialin [（-）-1]。除了（+）-和（-）-波西可林外，还获得了相应的1'-表位（+）-和（-）-表波西林。用（-）-boscialin [（-）-1]及其三种立体异构体进行了体外测定，以测试其对微生物，寄生虫和人成纤维细胞的活性。调查显示出对各种微生物和布鲁氏罗氏锥虫的活性，并且还揭示了对人类癌细胞的细胞毒性。

  DOI：

  10.1021/np970517x

文献信息

• Synthesis of labile all-trans-7,8,7′,8′-bis-acetylenic carotenoids by bi-directional Horner–Wadsworth–Emmons condensation
  作者：Belén Vaz、Noelia Fontán、Marta Castiñeira、Rosana Álvarez、Ángel R. de Lera

  DOI：10.1039/c4ob02144d

  日期：——

  Two symmetrical C₇,C₈-acetylenic carotenoids have been stereoselectively prepared using a bi-directional Horner–Wadsworth–Emmons condensation of the C₁₀-dialdehyde and C₁₅-phosphonates.

  两个对称的C₇,C₈-炔基类胡萝卜素已经通过使用C₁₀-二甲醛和C₁₅-磷酰化物的双向霍纳-沃兹沃斯-埃蒙斯缩合反应立体选择性地制备出来了。
• Reduction of Aliphatic and Aromatic Cyclic Ketones tosec-Alcohols by Aqueous Titanium Trichloride/Ammonia System. Steric Course and Mechanistic Implications
  作者：Angelo Clerici、Nadia Pastori、Ombretta Porta

  DOI：10.1002/1099-0690(200106)2001:12<2235::aid-ejoc2235>3.0.co;2-e

  日期：2001.6

  In contrast to the dissolved metal and metal hydride reductions, the reduction of cyclic ketones by the aqueous TiCl3/NH3 system favours the formation of the less thermodynamically stable axial alcohol. The ammonium ion formed in situ is essential for the reduction to proceed because it behaves as a mild Bronsted acid in basic medium and favours the protonation of the intermediate ketyl. The corresponding

  与溶解的金属和金属氢化物的还原相反，含水 TiCl3/NH3 系统对环酮的还原有利于形成热力学稳定性较差的轴向醇。原位形成的铵离子对于还原的进行是必不可少的，因为它在碱性介质中表现为温和的布朗斯台德酸，有利于中间体酮基的质子化。然后在发生第一次电子转移到底物的条件下，相应的 α-羟基自由基被迅速还原。我们建议立体选择性由第二个还原步骤决定，该步骤通过受阻较少的过渡态发生，而不管要还原的自由基在热力学上是否有利。
• Preparation of (1R,4S)-4-hydroxy-1,2,2-trimethylcyclopentyl methyl
  申请人：BASF Aktiengesellschaft

  公开号：US06111125A1

  公开（公告）日：2000-08-29

  A process for preparing 4-hydroxy-1,2,2-trimethylcyclopentyl methyl ketones of the general formula I, in particular of the (1R,4S)-4-hydroxy-1,2,2-trimethylcyclopentyl methyl ketone of the formula Ia ##STR1## which is required for preparing the red dye capsorubin which is in demand, starts from 2,2,6-trimethylcyclohexanones of the general formula II ##STR2## where R is hydrogen or a protective group, via the novel intermediates of the general formulae V and VI ##STR3## by diastereoselective epoxidation and reaction of the resulting 7-oxabicyclo[4.1.0]heptanes of the general formula VIII ##STR4## with Lewis acids and, where appropriate, removal of the protective group. Also claimed are the novel intermediates of the formula V and their (1S) and (1R) isomers and those of the formula VIII as well as their (1R,3S,6S), (1S,3S,6R) and (1R,3R,6S) isomers.

  一种制备一般式I的4-羟基-1,2,2-三甲基环戊基甲基酮的方法，特别是制备一般式Ia的(1R,4S)-4-羟基-1,2,2-三甲基环戊基甲基酮的方法，该方法用于制备需求量大的红色染料Capsorubin，从一般式II的2,2,6-三甲基环己酮开始，其中R是氢或保护基，通过新的一般式V和VI的中间体，通过对结果的7-氧杂双环[4.1.0]庚烷一般式VIII的选择性顺式环氧化和反应，与路易斯酸反应，并在适当情况下去除保护基。还要求一般式V的新型中间体及其(1S)和(1R)异构体，以及一般式VIII的中间体及其(1R,3S,6S)、(1S,3S,6R)和(1R,3R,6S)异构体。
• Cloning, Sequence Analysis, and Expression in Escherichia coli of the Gene Encoding Monovalent Cation-activated Levodione Reductase from Corynebacterium aquaticum M-13
  作者：Ayumi YOSHISUMI、Masaru WADA、Hiroshi TAKAGI、Sakayu SHIMIZU、Shigeru NAKAMORI

  DOI：10.1271/bbb.65.830

  日期：2001.1

  The gene encoding (6R)-2,2,6-trimethyl-1,4-cyclohexanedione (levodione) reductase was cloned from the genomic DNA of the soil isolate bacterium Corynebacterium aquaticum M-13. The gene contained an open reading frame consisting of 801 nucleotides corresponding to 267 amino acid residues. The deduced amino acid sequence showed approximately 35% identity with other short chain alcohol dehydrogenase/reductase (SDR) superfamily enzymes. The probable NADH-binding site and three catalytic residues (Ser-Tyr-Lys) were conserved. The enzyme was sufficiently produced in recombinant Escherichia coli cells using an expression vector pKK223-3, and purified to homogeneity by two-column chromatography steps. The enzyme purified from E. coli catalyzed stereo- and regio-selective reduction of levodione, and was strongly activated by monovalent cations, such as K+, Na+, and NH4+, as was the case of that from C. aquaticum M-13. To our knowledge, this is the first sequencing report of a monovalent cation-activated SDR enzyme.

  编码（6R）-2,2,6-三甲基-1,4-环己二酮（左旋酮）还原酶的基因是从土壤分离菌Corynebacterium aquaticum M-13的基因组DNA中克隆得到的。该基因包含一个开放阅读框，由801个核苷酸组成，对应267个氨基酸残基。推导出的氨基酸序列与其他短链醇脱氢酶/还原酶（SDR）超家族酶显示出大约35%的同源性。可能的NADH结合位点和三个催化残基（Ser-Tyr-Lys）是保守的。该酶在重组大肠杆菌中使用表达载体pKK223-3产生，经过两步柱层析纯化到均一状态。从大肠杆菌中纯化的酶催化了左旋酮的立体选择性和区域选择性还原，并且受到单价阳离子如K+、Na+和NH4+的强烈激活，这与C. aquaticum M-13中的酶情况相同。我们所知，这是第一个关于单价阳离子激活的SDR酶的序列报告。
• Synthesis of (3S,3′S)- and meso-Stereoisomers of Alloxanthin and Determination of Absolute Configuration of Alloxanthin Isolated from Aquatic Animals
  作者：Yumiko Yamano、Takashi Maoka、Akimori Wada

  DOI：10.3390/md12052623

  日期：——

  In order to determine the absolute configuration of naturally occurring alloxanthin, a HPLC analytical method for three stereoisomers 1a–c was established by using a chiral column. Two authentic samples, (3S,3′S)- and meso-stereoisomers 1b and 1c, were chemically synthesized according to the method previously developed for (3R,3′R)-alloxanthin (1a). Application of this method to various alloxanthin specimens of aquatic animals demonstrated that those isolated from shellfishes, tunicates, and crucian carp are identical with (3R,3′R)-stereoisomer 1a, and unexpectedly those from lake shrimp, catfish, biwa goby, and biwa trout are mixtures of three stereoisomers of 1a–c.

  为了确定天然存在的全黄素的绝对构型，采用手性柱建立了三种立体异构体1a–c的HPLC分析方法。根据之前为(3R,3′R)-全黄素(1a)开发的方法，化学合成了两个认证样品，即(3S,3′S)-和meso立体异构体1b和1c。将该方法应用于多种水生动物的全黄素样品表明，从贝类、 Tunicates和鲤鱼中分离出的全黄素与(3R,3′R)-立体异构体1a相同，而意外的是，从湖虾、鲇鱼、琵琶鲽和琵琶鳟中分离出的样品则是三种立体异构体1a–c的混合物。