siphonarienal | 156162-12-8

• 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: siphonarienal
• 英文别名: (E,4S,6S,8S)-2,4,6,8-tetramethylundec-2-enal
• CAS: 156162-12-8
• 化学式: C₁₅H₂₈O
• 分子量: 224.387
• InChiKey: HRYWLSLFUYLTSR-GHJWDUABSA-N

物化性质

• 沸点：
  301.3±11.0 °C(Predicted)
• 密度：
  0.837±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  siphonarienal 在 2,6-二甲基吡啶 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.25h， 生成 (2S,4R,5S,6E,8S,10S,12S)-2-benzoyloxy-5-(tert-butyldimethylsilyloxy)-4,6,8,10,12-pentamethyl-pentadec-6-en-3-one
  参考文献：
  名称：

  Efficient and Selective Synthesis of Siphonarienolone and Related Reduced Polypropionates via Zr-Catalyzed Asymmetric Carboalumination

  摘要：

  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.

  DOI：

  10.1021/ol0497483
• 作为产物：
  描述：

  (2S,4S,3R,5R,6S)-3,5-dihydroxy-N-methoxy-N,2,4,6-tetramethylnonanamide 在 4-二甲氨基吡啶 、 manganese(IV) oxide 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 lithium aluminium tetrahydride 、 碘苯二乙酸 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 吡啶 、 乙醚 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 16.0h， 生成 siphonarienal
  参考文献：
  名称：

  Catalytic, Asymmetric Synthesis of Siphonarienal

  摘要：

  This paper describes the synthesis of the marine natural product, siphonarienal. The key step of this synthesis is an aldol reaction that constructs most of the skeleton and sets all three stereocenters of the target in one step from commercially available starting materials. Deoxygenation and chain homologation steps complete the synthesis.

  DOI：

  10.1021/jo0160367

文献信息

• Preparation of Optically Enriched Secondary Alkyllithium and Alkylcopper Reagents—Synthesis of (−)‐Lardolure and Siphonarienal
  作者：Varvara Morozova、Juri Skotnitzki、Kohei Moriya、Konstantin Karaghiosoff、Paul Knochel

  DOI：10.1002/anie.201800792

  日期：2018.5.4

  converted into secondary alkyllithium and secondary alkylcopper compounds with very high retention of configuration. Quenching with various electrophiles, including chiral epoxides, provided a range of chiral molecules with high enantiomeric purity (>90 % ee). This method has been applied in an iterative fashion in the total synthesis of (−)‐lardolure in 13 steps and 5.4 % overall yield (>99 % ee, dr>99:1)

  将光学富集的仲烷基碘化物转化为仲烷基锂和仲烷基铜化合物，并保持很高的构型。用包括手性环氧化物在内的各种亲电试剂进行猝灭，提供了一系列具有高对映体纯度（> 90％ee）的手性分子 。该方法已以迭代方式应用在（-）-lardolure的总合成中，共13步，总收率5.4％（> 99％  ee，dr> 99：1）和siphonarienal在15步中，总收率5.6％（ > 99％  ee，dr> 99：1）从市售的（R）-3-羟基丁酸乙酯（> 99％  ee）开始。
• Divergent Enantioselective Total Synthesis of Siphonarienal, Siphonarienone, and Pectinatone
  作者：Jhillu Singh Yadav、D. Narasimha Chary、Nagendra Nath Yadav、Sandip Sengupta、Basi V. Subba Reddy

  DOI：10.1002/hlca.201300035

  日期：2013.10

  A divergent synthesis of siphonarienal, siphonarienone, and pectinatone has been achieved from a common precursor 4, which was synthesized by using an enzymatic desymmetrization approach. The major key steps involved were Grignard reaction, Wittig reaction, Evans' asymmetric alkylation, and base‐catalyzed cyclization.

  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。
• Isolation and synthesis of siphonarienal a new polypropionate from Siphonaria grisea
  作者：Manuel Norte、José J. Fernández、Agustín Padilla

  DOI：10.1016/s0040-4039(00)76923-1

  日期：1994.5

  Siphonarienal 1, a pentapropionate derivative, was isolated from the marine pulmonate mollusk Siphonaria grisea. Its structure was established on the basis of its spectroscopic data and its absolute configuration was assured by its enantioselective synthesis.

  Siphonarienal 1，一个五丙酸酯衍生物，从海洋软体动物有肺分离Siphonaria菌。根据其光谱数据确定其结构，并通过对映选择性合成确保其绝对构型。
• Application of Conformation Design in Acyclic Stereoselection:  Total Synthesis of Borrelidin as the Crystalline Benzene Solvate
  作者：Stephen Hanessian、Yang、Simon Giroux、Vincent Mascitti、Jianguo Ma、Franck Raeppel

  DOI：10.1021/ja030139k

  日期：2003.11.1

  The total synthesis of (-)-borrelidin (treponemycin), a structurally distinct 18-membered macrolide antibiotic, has been achieved. It was isolated as the crystalline benzene solvate, and its structure was confirmed by a single-crystal X-ray analysis. The deoxypropionate subunit consisting of four alternating C-methyl groups with a C(4)-C(10) syn/syn/anti orientation was elaborated by a new method of

  (-)-疏螺旋体素（密螺旋体霉素）的全合成，一种结构独特的 18 元大环内酯抗生素，已经实现。它被分离为结晶苯溶剂化物，其结构由单晶 X 射线分析证实。脱氧丙酸亚基由四个交替的 C-甲基基团组成，具有 C(4)-C(10) 顺/顺/反取向，是通过一种新方法对无环 α、β-不饱和酯进行迭代加成，依赖于两个连续的1,3-诱导并以 d-甘油醛作为手性祖体开始。独特的 Z/E 氰基二烯单元是通过应用 Still-Gennari 烯化协议作为单一异构体获得的。γ-羟基环戊烷羧酸亚单元由 L-苹果酸利用 C-乙烯基和 C-烯丙基的顺序引入制备，通过 Grubbs 闭环复分解反应利用无环 α,β-不饱和酯中的 1,2-诱导和碳环化。铜酸盐添加物中 1,3-syn-disposed 脱氧丙酸酯三联体的普遍性基于最小化过渡态中的同戊烷相互作用而合理化。虚拟金刚石晶格被用作描绘无环基材的低能量构象的可视化工具，并通过
• Asymmetric total synthesis of a putative sex pheromone component from the parasitoid wasp <i>Trichogramma turkestanica</i>
  作者：Danny Geerdink、Jeffrey Buter、Teris A van Beek、Adriaan J Minnaard

  DOI：10.3762/bjoc.10.71

  日期：——

  Virgin females of the parasitoid wasp Trichogramma turkestanica produce minute amounts of a sex pheromone, the identity of which has not been fully established. The enantioselective synthesis of a putative component of this pheromone, (6S,8S,10S)-4,6,8,10-tetramethyltrideca-2E,4E-dien-1-ol (2), is reported as a contribution to this identification. Catalytic asymmetric conjugate addition of methylmagnesium bromide and stereoselective Horner–Wadsworth–Emmons olefinations are used as the key steps, and 2 was obtained in 16 steps with an overall yield of 4.4%.

  寄生性蜂Trichogramma turkestanica的处女雌性产生微量的性信息素，其身份尚未完全确定。这篇文章报告了一种假定为该信息素成分的(6S,8S,10S)-4,6,8,10-四甲基十三烯-2E,4E-二醇(2)的对映选择性合成，作为对其鉴定的贡献。催化不对称共轭加成甲基溴化镁和立体选择性Horner–Wadsworth–Emmons烯烃化反应被用作关键步骤，2经过16个步骤得到，总收率为4.4%。