(Z,2S)-2-[tert-butyl(dimethyl)silyl]oxydec-4-enal | 83685-90-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z,2S)-2-[tert-butyl(dimethyl)silyl]oxydec-4-enal
• CAS: 83685-90-9
• 化学式: C₁₆H₃₂O₂Si
• 分子量: 284.514
• InChiKey: VABPBQIUDPQHKT-SSCKCOOKSA-N

物化性质

• 沸点：
  315.7±30.0 °C(Predicted)
• 密度：
  0.872±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z,2S)-2-[tert-butyl(dimethyl)silyl]oxydec-4-enal 在 nickel dichloride chromium dichloride 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 34.5h， 生成 solandelactone E
  参考文献：
  名称：

  从水生Solanderia secunda合成solandelactones E和F，类同二十烷酸。

  摘要：

  内酯内酯E和F的不对称总合成证实，这些羟脂在C11处的羟基构型分配有误，并且该中心的立体化学应颠倒。合成中的关键步骤涉及Nagao不对称乙酸酯醛醇醛缩醛反应，定向Simmons-Smith环丙烷化，Holmes-Claisen重排以建立不饱和八内酯，以及Nozaki-Hiyama-Kishi偶联以连接C11-C12的两个主要片段。

  DOI：

  10.1021/ol701564x
• 作为产物：
  描述：

  methyl (S)-3-(tert-butyldimethylsilanyloxy)-4-(trityloxy)butanoate 在 甲酸 、 四丙基高钌酸铵 、 4 A molecular sieve 、 sodium hexamethyldisilazane 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 2.33h， 生成 (Z,2S)-2-[tert-butyl(dimethyl)silyl]oxydec-4-enal
  参考文献：
  名称：

  从水生Solanderia secunda合成solandelactones E和F，类同二十烷酸。

  摘要：

  内酯内酯E和F的不对称总合成证实，这些羟脂在C11处的羟基构型分配有误，并且该中心的立体化学应颠倒。合成中的关键步骤涉及Nagao不对称乙酸酯醛醇醛缩醛反应，定向Simmons-Smith环丙烷化，Holmes-Claisen重排以建立不饱和八内酯，以及Nozaki-Hiyama-Kishi偶联以连接C11-C12的两个主要片段。

  DOI：

  10.1021/ol701564x

文献信息

• Total Synthesis of Marine OxylipinsConstanolactone A and B
  作者：Jörg Pietruszka、Thorsten Wilhelm

  DOI：10.1055/s-2003-40986

  日期：——

  A short, high-yielding synthesis of the marine oxylipins constanolactoneA and B was reported. Starting from cinnamyl alcohol (3), the cylopropyl lactone moiety 2 was obtained in 28% yield (11steps). The second coupling partner, vinyl iodide 1,was isolated in 7 steps and 32% yield. Chromium mediatedaddition yielded the natural products as a 2:1 mixture (74%).

  报道了一种短小且高产率的海洋氧脂肪酸化合物constanolactone A和B的合成。从肉桂醇（3）出发，获得了环丙基内酯部分2，产率为28%（共11步）。第二个偶联伙伴，乙烯碘化物1，经过7步合成，产率为32%。铬介导的加成反应生成了自然产物的2:1混合物，产率为74%。
• Total Synthesis of Solandelactones A, B, E, and F Exploiting a Tandem Petasis−Claisen Lactonization Strategy
  作者：James D. White、Christopher M. Lincoln、Jongtae Yang、William H. C. Martin、David B. Chan

  DOI：10.1021/jo800335g

  日期：2008.6.1

  Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyania-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C(22) oxylipins that parallels a hypothesis put forward previously to explain the origin of C(20) cyclopropane-containing algal products.
• (<i>R</i>)-2,3-<i>O</i>-Cyclohexylideneglyceraldehyde, a Versatile Intermediate for Asymmetric Synthesis of Homoallyl and Homopropargyl Alcohols in Aqueous Medium
  作者：Angshuman Chattopadhyay

  DOI：10.1021/jo9604696

  日期：1996.1.1

  Zn-mediated allylation and propargylation of (R)-2,3-O-cyclohexylideneglyceraldehyde (1) in aqueous medium following Luche's procedure afforded the anti homoallylic 3 and homopropargylic 8 alcohols in good yield and with high stereoselectivity, Crotylation of 1 under similar conditions afforded appreciable amounts of erythro-5 and threo-6 alcohols. In each case, the diastereo alcohols are separable by column chromatography. Compound 8 on appropriate chemical manipulation of its functionalities gave the (S)-enantiomer of (R)-13, a useful synthon of LTB(4). Compound 3 on chemical elaboration afforded a diversely functionalized triol derivative 15, a potentially useful synthon for many bioactive compounds.
• Total Synthesis of Solandelactones E and F, Homoeicosanoids from the Hydroid <i>Solanderia </i><i>secunda</i>
  作者：James D. White、William H. C. Martin、Christopher Lincoln、Jongtae Yang

  DOI：10.1021/ol701564x

  日期：2007.8.1

  Asymmetric total syntheses of solandelactones E and F confirmed that hydroxyl configuration at C11 in these oxylipins had been misassigned and that the stereochemistry at this center should be reversed. Key steps in the synthesis involved a Nagao asymmetric acetate aldol reaction, a directed Simmons-Smith cyclopropanation, a Holmes-Claisen rearrangement to establish the unsaturated octalactone, and

  内酯内酯E和F的不对称总合成证实，这些羟脂在C11处的羟基构型分配有误，并且该中心的立体化学应颠倒。合成中的关键步骤涉及Nagao不对称乙酸酯醛醇醛缩醛反应，定向Simmons-Smith环丙烷化，Holmes-Claisen重排以建立不饱和八内酯，以及Nozaki-Hiyama-Kishi偶联以连接C11-C12的两个主要片段。