(4E,6S,8S,10S)-4,6,8,10-tetramethyl-4-tridecen-3-one | 128008-15-1

• 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: (4E,6S,8S,10S)-4,6,8,10-tetramethyl-4-tridecen-3-one
• 英文别名: (4E,6S,8S,10S)-4,6,8,10-tetramethyltridec-4-en-3-one；(6S,8S,10S,E)-4,6,8,10-tetramethyltridec-4-en-3-one；(+)-siphonarienone；Siphonarienone；(E,6S,8S,10S)-4,6,8,10-tetramethyltridec-4-en-3-one
• CAS: 128008-15-1
• 化学式: C₁₇H₃₂O
• 分子量: 252.44
• InChiKey: LRJDUFSHRXSRLR-IZGRLVBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (2S,4R)-5-(tert-butyl(dimethyl)silyloxy)-2,4-dimethyl-1-pentanol 在 4-二甲氨基吡啶 、 锂硼氢 、 草酰氯 、 2-碘苯甲酸 、 lithium hydrochloride monohydrate 、 palladium 10% on activated carbon 、 四丁基氟化铵 、 氢气 、 三甲基乙酰氯 、 sodium hydride 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 magnesium 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 乙酸乙酯 、 甲苯 、 mineral oil 、 苯 为溶剂， 反应 58.41h， 生成 (4E,6S,8S,10S)-4,6,8,10-tetramethyl-4-tridecen-3-one
  参考文献：
  名称：

  虹吸烯醛，虹吸烯酮和果胶的对映异构全选择性合成

  摘要：

  从共同的前体4获得了虹吸烯醛，虹吸烯酮和果胶酮的发散合成，该前体4是通过酶促脱对称方法合成的。涉及的主要关键步骤是格利雅（Grignard）反应，维蒂希（Wittig）反应，埃文斯（Evans）的不对称烷基化和碱催化的环化反应。

  DOI：

  10.1002/hlca.201300035

文献信息

• Synthesis of (+)-siphonarienone: Asymmetric alkylation using a chiral benzopyrano-isoxazolidine auxiliary
  作者：Atsushi Abiko、Satoru Masamune

  DOI：10.1016/0040-4039(95)02353-4

  日期：1996.2

  Asymmetric alkylation of the potassium enolates derived from N-propionyl benzopyrano-[4,3-c]-isoxazolidine derivatives with chiral alkyl triflates proceeded smoothly with high diastereoselectivity. The stereochemistry of the newly formed stereogenic center was fully controlled by the facial selectivity of the enolate according to the rule of double asymmetric synthesis. The application of this methodology

  N-丙酰基苯并吡喃基-[4,3-c]-异恶唑烷衍生物衍生的烯醇钾与手性烷基三氟甲磺酸酯的不对称烷基化以高非对映选择性顺利进行。根据双不对称合成的规则，新形成的立体异构中心的立体化学完全受烯醇化物的面部选择性控制。这种方法学的应用导致了海洋聚丙烯酸酯天然产物（+）-siphonarienoneone的首次合成。
• Total synthesis of the marine polypropionates, siphonarienal, siphonarienone, and pectinatone
  作者：Gowravaram Sabitha、Peddabuddi Gopal、Jhillu S. Yadav

  DOI：10.1016/j.tetasy.2009.08.021

  日期：2009.10

  The synthesis of the marine natural products, siphonarienal, siphonarienone, and pectinatone is described employing desymmetrization strategy to create three consecutive stereogenic centers. The key intermediate 7 was made by asymmetric hydroboration of the known meso-olefin using (−)-IPC2BH followed by PCC and Baeyer-Villiger oxidation reactions.

  利用去对称化策略创建了三个连续的立体生成中心，介绍了海洋天然产物虹吸管烯醛，虹吸管烯酮和果胶酮的合成。关键中间体7是通过使用（-）-IPC 2 BH对已知内消旋烯烃进行不对称硼氢化，然后进行PCC和Baeyer-Villiger氧化反应制得的。
• Stereoselective syntheses of siphonarienal and siphonarienone
  作者：Supriya Ghanty、Chinta Krinda Suresh Kumar、B.V. Subba Reddy

  DOI：10.1016/j.tetasy.2015.07.001

  日期：2015.9

  The asymmetric total synthesis of marine polypropionate natural products siphonarienal and siphonarienone has been achieved from a common precursor 3. The key transformations of this synthesis are the diastereoselective oxidative kinetic resolution, Wittig olefination, Grignard reaction, and Evans asymmetric alkylation for the installation of a third stereogenic center of the target molecules from

  船用聚丙烯酸酯天然产物siphonarienal和siphonarienoneone的不对称全合成已从常见的前体3中获得。该合成的关键转变是非对映选择性氧化动力学拆分，Wittig烯烃化，Grignard反应和Evans不对称烷基化，用于从可商购的原材料中安装靶分子的第三个立体异构中心。
• A Highly Catalytic Asymmetric Conjugate Addition:  Synthesis of the C14−C20 Fragment of Antibiotic TMC-151A, Siphonarienal and Siphonarienone
  作者：Tze-Keong Lum、Shun-Yi Wang、Teck-Peng Loh

  DOI：10.1021/ol702715q

  日期：2008.3.1

  A highly selective and general method for the synthesis of enantiopure deoxypropionates via the iterative application of CuI-ToI-BINAP-catalyzed asymmetric conjugate addition is described. This method gives access to all possible stereoisomers since both syn- and anti-deoxypropionates were obtained in high diastereoselectivities. The usefulness of the method is further exemplified by the preparation of two marine organisms, siphonarienal and siphonarienone, from commercially available trans-2-hexenoate.
• Efficient and Selective Synthesis of Siphonarienolone and Related Reduced Polypropionates via Zr-Catalyzed Asymmetric Carboalumination
  作者：Marina Magnin-Lachaux、Ze Tan、Bo Liang、Ei-ichi Negishi

  DOI：10.1021/ol0497483

  日期：2004.4.1

  Siphonarienolone (1) has been synthesized from siphonarienal (3) in 66% over four steps. Synthesis of 3, in turn, has been achieved in two steps (85% combined yield) from 4, prepared from 3-buten-1-ol in seven steps (23% combined yield). Also, a two-step conversion of 3 into siphonarienone (2) is reported.