(2Z,4S)-2-octen-4-ol | 105087-07-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2Z,4S)-2-octen-4-ol
• 英文别名: (4S,2Z)-2-octen-4-ol；(Z,4S)-oct-2-en-4-ol
• CAS: 105087-07-8
• 化学式: C₈H₁₆O
• 分子量: 128.214
• InChiKey: WGDUEFYADBRNKG-RZAAKKIOSA-N

物化性质

• 沸点：
  175.0±0.0 °C(Predicted)
• 密度：
  0.843±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2Z,4S)-2-octen-4-ol 在 正丁基锂 、 四甲基乙二胺 、 potassium tert-butylate 、 copper (I) acetate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 8.0h， 生成 (E)-2-(5-methyl-6-undecen-1-yl)-1,3-dioxane
  参考文献：
  名称：

  Reversible 1,3-anti/syn-Stereochemical Courses in Copper-Catalyzed γ-Selective Allyl–Alkyl Coupling between Chiral Allylic Phosphates and Alkylboranes

  摘要：

  The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with gamma-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.

  DOI：

  10.1021/ja302520h
• 作为产物：
  描述：

  (1S)-1-[(2R,3S)-3-butyl-2-trimethylsilyloxiran-2-yl]ethanol 在 aluminium hydride 、 六甲基磷酰三胺 、 正丁基锂 作用下， 以 乙醚 为溶剂， 反应 1.0h， 生成 (2Z,4S)-2-octen-4-ol
  参考文献：
  名称：

  Synthesis of optically active .beta.,.gamma.-epoxy alcohols and secondary allylic alcohols via diastereoselective addition of .alpha.-(trimethylsilyl)-.alpha.,.beta.-epoxy aldehydes with organometallic compounds

  摘要：

  DOI：

  10.1021/jo00374a047

文献信息

• Palladium-Catalyzed γ-Selective and Stereospecific Allyl−Aryl Coupling between Acyclic Allylic Esters and Arylboronic Acids
  作者：Hirohisa Ohmiya、Yusuke Makida、Dong Li、Masahito Tanabe、Masaya Sawamura

  DOI：10.1021/ja9092264

  日期：2010.1.20

  Reactions between acyclic (E)-allylic acetates and arylboronic acids in the presence of a palladium catalyst prepared from Pd(OAc)(2), phenanthroline (or bipyridine), and AgSbF(6) (1:1.2:1) proceeded with excellent gamma-selectivity to afford allyl-aryl coupling products with E-configuration. The reactions of alpha-chiral allylic acetates took place with excellent alpha-to-gamma chirality transfer

  在由 Pd(OAc)(2)、菲咯啉（或联吡啶）和 AgSbF(6) (1:1.2:1) 制备的钯催化剂存在下，无环 (E)-烯丙基乙酸酯和芳基硼酸之间的反应进行得非常好γ-选择性提供具有 E-构型的烯丙基-芳基偶联产物。α-手性烯丙基乙酸酯的反应发生了具有顺式立体化学的优异的 α 到 γ 手性转移，以​​产生在苄基位置具有立体中心的烯丙基化芳烃。该反应在烯丙基乙酸酯和芳基硼酸中都可以耐受范围广泛的官能团。此外，肉桂醇衍生物的γ-芳基化得到含有未共轭烯基取代基的墒二芳基烷烃衍生物。该方法的合成效用通过其在 (+)-舍曲林（一种抗抑郁药）的有效合成中的应用得到证明。观察到的 γ-区域选择性和 E-1,3-syn 立体化学基于 Pd(II) 机制进行合理化，该机制涉及阳离子单（酰氧基）钯（II）配合物和芳基硼​​酸之间的金属转移，以及定向碳钯化，然后是 Syn-β -酰氧基消除。与可能的中间体相
• Copper-Catalyzed γ-Selective and Stereospecific Allylic Alkylation of Ketene Silyl Acetals
  作者：Dong Li、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/ja111645q

  日期：2011.4.20

  Copper-catalyzed allylic alkylation of ketene silyl acetals proceeded with excellent γ-E-selectivity. Efficient α-to-γ chirality transfer with anti-selectivity occurred in the reaction of enantioenriched secondary allylic phosphates, affording enantioenriched β-branched γ,δ-unsaturated esters. Excellent functional group compatibility was observed.

  铜催化烯酮甲硅烷基缩醛的烯丙基烷基化以优异的γ-E-选择性进行。在对映体富集的仲烯丙基磷酸酯的反应中发生了具有抗选择性的高效 α 到 γ 手性转移，得到对映体富集的 β-支链 γ,δ-不饱和酯。观察到优异的官能团相容性。
• Copper-Catalyzed γ-Selective and Stereospecific Allyl−Aryl Coupling between (<i>Z</i>)-Acyclic and Cyclic Allylic Phosphates and Arylboronates
  作者：Hirohisa Ohmiya、Natsumi Yokokawa、Masaya Sawamura

  DOI：10.1021/ol100841y

  日期：2010.5.21

  A Cu-catalyzed allyl−aryl coupling reaction between (Z)-acyclic or cyclic allylic phosphates and arylboronates proceeds with excellent γ-E-selectivity and 1,3-anti chirality transfer, which gives the corresponding coupling products with benzylic and allylic stereogenic centers. The wide availability and easy-to-handle nature of arylboronates, the inexpensiveness of the Cu catalyst system, and the high

  （Z）-无环或环状烯丙基磷酸酯与芳基硼酸酯之间的Cu催化的烯丙基-芳基偶联反应具有出色的γ-E-选择性和1,3-抗手性转移，从而产生了具有苄基和烯丙基立体异构中心的相应偶联产物。芳基硼酸酯的广泛可用性和易于处理的性质，Cu催化剂体系的廉价以及高区域选择性和立体选择性是该方案的吸引人的特征。
• Enantioselective addition of (Z)- and (E)-alkenylzinc bromides to aldehydes: asymmetric synthesis of sec-allylalcohols
  作者：Wolfgang Oppolzer、Rumen N. Radinov

  DOI：10.1016/s0040-4039(00)93553-6

  日期：1991.10

  In situ prepared (Z)- and (E)-1-alkenylzinc bromides 5 were added to various aldehydes 1 in the presence of lithiated (+)-N-methylephedrine or (+)-2-(N,N-dimethylamino)-1,2-diphenylethanol to give sec. allyalcohols 7 in high optical purity with simple recovery of the chiral aminol 6.

  在锂化的（+）- N-甲基麻黄碱或（+）-2-（N，N-二甲基氨基）-的存在下，将原位制备的（Z）-和（E）-1-烯基溴化锌5添加到各种醛1中。 1,2-二苯乙醇给出sec。高光学纯度的烯丙基醇7与手性氨基6的简单回收。
• Highly Stereoselective Anti S_N2‘ Substitutions of (<i>Z</i>)-Allylic Pentafluorobenzoates with Polyfunctionalized Zinc−Copper Reagents
  作者：Nicole Harrington-Frost、Helena Leuser、M. Isabel Calaza、Florian F. Kneisel、Paul Knochel

  DOI：10.1021/ol034525i

  日期：2003.6.1

  [GRAPHICS]Allylic substitution reactions of zinc-copper organometallics on (Z)-allylic pentafluorobenzoates proceed with very high regioselectivity and excellent anti selectivity. The high fidelity in transfer of stereochemical information allowed a short synthesis of (+)-ibuprofen (97% ee).