(E)-2-methyl-1-phenyl-2,4-pentadiene | 132592-66-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-2-methyl-1-phenyl-2,4-pentadiene
• 英文别名: [(2E)-2-methylpenta-2,4-dienyl]benzene
• CAS: 132592-66-6
• 化学式: C₁₂H₁₄
• 分子量: 158.243
• InChiKey: PCNBUBPRQUQMDV-YRNVUSSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2-甲基-戊-1,4-二烯-3-醇 在 CuCN 作用下， 以 乙醚 为溶剂， 生成 (E)-2-methyl-1-phenyl-2,4-pentadiene
  参考文献：
  名称：

  Alkylation of allylic derivatives. 17. Cross-coupling reactions of diallylic pivalates with butyl- and phenylcopper reagents

  摘要：

  Cross coupling (Z)-1-phenyl-1,4-pentadien-3-yl pivalate (cis-1-OPiv) with LiCuBu2, LiCu(CN)Bu, LiCuPh2, and LiCu(CN)Ph gives only the fully conjugated gamma-coupling product. With LiCuBu2, substantial loss of double-bond configuration occurs to give primarily the all-trans coupling product. With other cuprates, no detectable loss of double-bond configuration was observed. Cross coupling (Z)-3-(2-phenylethenyl)2-cyclohexen-1-yl pivalate (cis-18-OPiv) with LiCuBu2, LiCuPh2, and LiCu(CN) ph gives only alpha-coupling product; with LiCu(CN)Bu, a mixture of alpha, gamma, and epsilon coupling product was obtained. Cross coupling with LiCuBu2, results in loss of double-bond configuration in the alpha-alkylation product. With the other cuprates, no loss of double-bond configuration was detected in the alpha and gamma coupling product. These results have profound mechanistic implications, which are discussed. The relationship between structure and reactivity was also investigated. A variety of diallylic pivalates (1-5 OPiv) were prepared and cross coupled with LiCuBu2, LiCu(CN)Bu, LiCuPh2, and LiCu(CN)Ph. Generally, coupling occurs at the least-substituted allylic system; mechanistic implications are discussed.

  DOI：

  10.1021/jo00007a055

文献信息

• (<i>E</i>)- and (<i>Z</i>)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes:  Synthetic Equivalents for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion
  作者：Timothy P. Meagher、Larry Yet、Chi-Nung Hsiao、Harold Shechter

  DOI：10.1021/jo970545k

  日期：1998.6.1

  (E)- and (Z)-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (7 and 8) are converted by n-BuLi to (E)- and (Z)-1-lithio-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (15 and 16) with retention of initial stereochemistries. Reactions of 15 and 16 with electrophiles (protio and deuterio acids, primary, secondary, and benzyl halides, chloroformates, chlorothioformates, acid chlorides, epoxides, trialkylsilyl chlorides, and triethylgermanyl chloride) in THF or THF/HMPA give the corresponding (E)- and (Z)-1-(phenylsulfonyl)-1-substituted-4-(trimethylsilyl)-2-butenes (32) with stereochemical retention. That beta,gamma-unsaturated silyl sulfones 32 are formed instead of their alpha,beta-unsaturated (conjugated) isomers are attributed to stabilizing multiple anionic and cationic hyperconjugation and to steric effects as in 29-31. Of importance in synthesis is that 32 are eliminated by TBAF at -20 to 0 degrees C, thermally, or by column chromatography to (E)- (100 to > 93%) rather than (Z)-1-substituted-1,3-butadienes (38). Further, 32 undergo conversions by n-BuLi and various alkylating agents to (unconjugated) 1-(phenylsulfonyl)-1,1-disubstituted-4-(trimethylsilyl)-2-butenes (46) with retention of stereochemistry; Eliminations of 46 by fluoride ion, acid catalysis, or heat yield 1,1-disubstituted-1,3-butadienes (53). Silyl sulfones 7 and 8 are thus synthetic equivalents for the (E)-1-(1,3-butadienyl) anion (44) and the 1,1-(1,3-butadienyl) dianion(57). Silyl sulfones 7 and 8 also undergo efficient stereospecific intramolecular conversions by n-BuLi and alpha,omega-dihalides to 1,1-cycloalka-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (62 and 71) that are eliminated by fluoride ion, heat, or adsorption chromatography to 1,1-cycloalka-1,3-butadienes (72).

  (E)- 和 (Z)-1-（苯砜基）-4-（三甲基硅基）-2-丁二烯（7 和 8）通过 n-BuLi 转化为 (E)- 和 (Z)-1- Chunky -1-（苯砜基）-4-（三甲基硅基）-2-丁二烯（15 和 16），并保留了初始立体化学。15 和 16 与电rophiles（质子和 Deuterio 酸、一级、二级、苯基卤素、氯仿酸、氯砜酸、酸酐、醚、三甲基硅基氯化物和三乙基 germanium 氯化物）在 THF 或 THF/HMPA 中反应，产生对应的 (E)- 和 (Z)-1-（苯砜基）-1-取代的-4-（三甲基硅基）-2-丁二烯（32），并保留了立体化学。由于β,γ-未饱和硅基硫醇 32 比其 α,β-未饱和（共轭）异构体更稳定，是因为它们通过多个 anionic 和 cationic 力的结合。 在合成中很重要的是，32 可以通过 TBAF 在 -20 到 0°C 的温度下脱除，或者通过柱状色谱从 (E)-（>93% 到 100%）转化为 1-取代-1,3-丁二烯（38）。此外，32 还可以通过 n-BuLi 和各种烷化剂转化为（非共轭）1-（苯基硫醇）-1,1-双取代的-4-（三甲基硅基）-2-丁二烯（46），保留立体化学。46 消除后通过氟离子、酸性催化或加热产生 1,1-取代-1,3-丁二烯（53）。 因此，7 和 8 的硅基硫醇是生成（E）-1-（1,3-丁二烯基）阴离子（44）和 1,1-（1,3-丁二烯基）二阴离子（57）的合成等效物。此外，7 和 8 还在 n-BuLi 和 alpha,omega-二卤物的参与下发生高效的立体选择性 intramolecular 转化，生成 1,1-环状结构化的-（苯基硫醇）-4-（三甲基硅基）-2-丁二烯（62 和 71），并通过氟离子、加热或吸附色谱法消除，得到 1,1-环状结构化的-1,3-丁二烯（72）。
• UNDERINER, TED L.;GOERING, HARLAN L., J. ORG. CHEM., 56,(1991) N, C. 2563-2572
  作者：UNDERINER, TED L.、GOERING, HARLAN L.

  DOI：——

  日期：——
• Alkylation of allylic derivatives. 17. Cross-coupling reactions of diallylic pivalates with butyl- and phenylcopper reagents
  作者：Ted L. Underiner、Harlan L. Goering

  DOI：10.1021/jo00007a055

  日期：1991.3

  Cross coupling (Z)-1-phenyl-1,4-pentadien-3-yl pivalate (cis-1-OPiv) with LiCuBu2, LiCu(CN)Bu, LiCuPh2, and LiCu(CN)Ph gives only the fully conjugated gamma-coupling product. With LiCuBu2, substantial loss of double-bond configuration occurs to give primarily the all-trans coupling product. With other cuprates, no detectable loss of double-bond configuration was observed. Cross coupling (Z)-3-(2-phenylethenyl)2-cyclohexen-1-yl pivalate (cis-18-OPiv) with LiCuBu2, LiCuPh2, and LiCu(CN) ph gives only alpha-coupling product; with LiCu(CN)Bu, a mixture of alpha, gamma, and epsilon coupling product was obtained. Cross coupling with LiCuBu2, results in loss of double-bond configuration in the alpha-alkylation product. With the other cuprates, no loss of double-bond configuration was detected in the alpha and gamma coupling product. These results have profound mechanistic implications, which are discussed. The relationship between structure and reactivity was also investigated. A variety of diallylic pivalates (1-5 OPiv) were prepared and cross coupled with LiCuBu2, LiCu(CN)Bu, LiCuPh2, and LiCu(CN)Ph. Generally, coupling occurs at the least-substituted allylic system; mechanistic implications are discussed.