(2E,6R)-2,6-dimethylocta-2,7-dienal | 177414-14-1

• 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: (2E,6R)-2,6-dimethylocta-2,7-dienal
• 英文别名: (6R,2E)-2,6-dimethyl-2,7-octadienal；(2e,6r)-(-)-2,6-Dimethylocta-2,7-dienal
• CAS: 177414-14-1
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: UVXVZRHRFYHHES-HZAKCSEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (2E,6R)-2,6-dimethylocta-2,7-dienal 在 platinum on activated charcoal 氢气 作用下， 以 甲醇 、 水 为溶剂， 反应 106.0h， 生成 (2R/S,6S)-(+)-2,6-dimethyl-1-octanol
  参考文献：
  名称：

  Terpenes in organic synthesis

  摘要：

  All four stereoisomers of 2,6-dimethyloctan-1-ol, the nearest precursors of the title formates, were synthesized in five to eight stages, with configurational purity ranging from 41 to 96 %, employing a stereodivergent scheme based on the partial hydrolysis of two pseudoracemic substrates, (2RS,6R)-2,6-dimethyloct-1-yl formate and (2RS,6S)-2,6-dimethyloct-1-yl acetate, in the presence of porcine pancreatic lipase (PPL). Configurations and diastereomeric compositions of the alcohols thus obtained were determined by correlating the latter with (S,S)-4,8-dimethyldecanal, prepared on the basis of enantioselective biohydrogenation of (R)-2,6-dimethylocta-2,7-dienal with bakers' yeast, and by comparing the [alpha](D) values of the alcohols with their NMR data and/or with those of their (S)-MTPA derivatives. The attractant potency of stereoisomeric 2,6-dimethyloct-1-yl formates towards Tribolium confusum was found to vary depending on their diastereomeric composition. The configuration at C(6) exerts some influence on the stereoselectivity of the PPL-catalyzed hydrolysis of pseudoracemic 2,6-dimethyloct-1-yl formates.

  DOI：

  10.1007/bf01433762
• 作为产物：
  描述：

  香茅烯 在 叔丁基过氧化氢 、 selenium(IV) oxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 72.0h， 以55%的产率得到(2E,6R)-2,6-dimethylocta-2,7-dienal
  参考文献：
  名称：

  动力学内酯化和接力闭环复分解环化反应全合成Peloruside A

  摘要：

  另一方面：描述了peloruside A( 1 )的收敛全合成。关键的策略特征是非对映选择性内酯化从C 2对称酮3生成 C5-C9 戊内酯，以及中继闭环复分解反应生成脱氢戊内酯2。鉴定了1的新异构体，即异戊内酯异戊内酯 A ( iso-1 )。MOM=甲氧基甲基。

  DOI：

  10.1002/anie.201002293

文献信息

• Tandem addition–cyclization mediated by sulfanyl radicals: a versatile strategy for iridoids synthesis
  作者：Elena M. Sánchez、Jesús F. Arteaga、Victor Domingo、José F. Quílez del Moral、M. Mar Herrador、Alejandro F. Barrero

  DOI：10.1016/j.tet.2008.03.058

  日期：2008.5

  Sulfanyl radicals trigger a tandem addition–cyclization protocol in linalool or citronelene derivatives for the efficient construction of the iridane monoterpene skeleton. Best results in yields and diastereoselectivity were obtained when phenylethylsulfanyl was used as radical initiator. We have proved the utility of this protocol with the enantiospecific synthesis of natural iridane dehydroiridomyrmecin

  硫烷基自由基在芳樟醇或香茅烯衍生物中触发串联加成-环化方案，以有效地构建铱单萜骨架。当使用苯基乙基硫烷基作为自由基引发剂时，可获得最佳的收率和非对映选择性结果。我们已经证明了该方案的实用性，它是从（-）-乙酸芳樟酯酯衍生物开始的对映体特异性合成天然环戊烷脱氢铱柔红霉素的，其分五步进行，总收率为28％。
• Total Synthesis of Peloruside A through Kinetic Lactonization and Relay Ring-Closing Metathesis Cyclization Reactions
  作者：Thomas R. Hoye、Junha Jeon、Lucas C. Kopel、Troy D. Ryba、Manomi A. Tennakoon、Yini Wang

  DOI：10.1002/anie.201002293

  日期：2010.8.16

  The other side: A convergent total synthesis of peloruside A (1) is described. The key strategic features are a diastereoselective lactonization to generate a C5–C9 valerolactone from the C2‐symmetric ketone 3, and a relay ring‐closing metathesis reaction to produce a dehydrovalerolactone 2. A new isomer of 1, the valerolactone isopeloruside A (iso‐1), was identified. MOM=methoxymethyl.

  另一方面：描述了peloruside A( 1 )的收敛全合成。关键的策略特征是非对映选择性内酯化从C 2对称酮3生成 C5-C9 戊内酯，以及中继闭环复分解反应生成脱氢戊内酯2。鉴定了1的新异构体，即异戊内酯异戊内酯 A ( iso-1 )。MOM=甲氧基甲基。
• Terpenes in organic synthesis
  作者：G. D. Gamalevich、B. N. Morozov、E. P. Serebryakov

  DOI：10.1007/bf01433762

  日期：1996.1

  All four stereoisomers of 2,6-dimethyloctan-1-ol, the nearest precursors of the title formates, were synthesized in five to eight stages, with configurational purity ranging from 41 to 96 %, employing a stereodivergent scheme based on the partial hydrolysis of two pseudoracemic substrates, (2RS,6R)-2,6-dimethyloct-1-yl formate and (2RS,6S)-2,6-dimethyloct-1-yl acetate, in the presence of porcine pancreatic lipase (PPL). Configurations and diastereomeric compositions of the alcohols thus obtained were determined by correlating the latter with (S,S)-4,8-dimethyldecanal, prepared on the basis of enantioselective biohydrogenation of (R)-2,6-dimethylocta-2,7-dienal with bakers' yeast, and by comparing the [alpha](D) values of the alcohols with their NMR data and/or with those of their (S)-MTPA derivatives. The attractant potency of stereoisomeric 2,6-dimethyloct-1-yl formates towards Tribolium confusum was found to vary depending on their diastereomeric composition. The configuration at C(6) exerts some influence on the stereoselectivity of the PPL-catalyzed hydrolysis of pseudoracemic 2,6-dimethyloct-1-yl formates.