2-Methyl-7-phenylhept-2-en-4-ol | 1428377-62-1

• 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: 2-Methyl-7-phenylhept-2-en-4-ol
• 英文别名: 2-methyl-7-phenylhept-2-en-4-ol
• CAS: 1428377-62-1
• 化学式: C₁₄H₂₀O
• 分子量: 204.312
• InChiKey: GAKYYPYPVNQKNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  2-Methyl-7-phenylhept-2-en-4-ol 在 4-二甲氨基吡啶 、 copper(I) bromide dimethylsulfide complex 、 N,N'-二环己基碳二亚胺 、 zinc(II) iodide 、 magnesium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 (6-methylhept-5-ene-1,4-diyl)dibenzene
  参考文献：
  名称：

  Allylic Substitution for Construction of a Chiral Quaternary Carbon Possessing an Aryl Group

  摘要：

  Phenylcopper reagents derived from 2:1 PhMgBr/Cu(acac)(2) and 3:1:1 PhMgBr/Cu(acac)(2)/ZnI2 were found to be highly reactive and regioselective in the allylic substitution of gamma,gamma-disubstituted secondary allylic picolinates designed for construction of a quaternary carbon, whereas the previous 2:1 ArMgBr/CuBr center dot Me2S reagent and that with ZnX2 were unsuccessful. The generality of the ArMgBr/Cu(acac)(2) reagent was examined with enantiomerically enriched allylic picolinates, which furnished quaternary carbons with high efficiency in >92% regioselectivity and >97% chirality transfer. Two cyclohexanes with a quaternary carbon were synthesized by using these reagents.

  DOI：

  10.1021/jo400248y
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 、 (3-phenylpropyl)magnesium chloride 以 四氢呋喃 为溶剂， 反应 2.0h， 以90%的产率得到2-Methyl-7-phenylhept-2-en-4-ol
  参考文献：
  名称：

  芳基锂衍生铜试剂用于γ,γ-二取代的仲烯丙基吡啶甲酸酯的四元立体中心形成烯丙基取代的探索

  摘要：

  用基于芳基锂的铜试剂对 γ,γ-二取代的仲烯丙基吡啶甲酸酯（2-PyCO2H 的酯）进行烯丙基取代以构建季碳。最初，2-methyl-7-phenylhept-2-en-4-yl picolinate 与衍生自苯基锂的苯基铜试剂在 1-3 中与 Cu(acac)2、Cu(OMe)2、CuBr·Me2S 和 CuCN 反应在存在过量溴化镁的情况下比例为 1。虽然形成了带有季碳的SN2'产物，但区域选择性最多为90%。相反，发现苯基锂/铜（I）噻吩-2-羧酸盐/溴化镁（Ph/Cu = 1.5–2:1，Mg/Li = >1）可产生 >98% 的区域选择性和足够的反应性。该系统成功地使用了八种芳基锂基铜试剂，这些试剂具有空间拥挤、给电子、或吸电子取代基。抗立体化学过程是通过使用对映体富集的香叶醛衍生的吡啶甲酸酯建立的。

  DOI：

  10.1055/s-0035-1560907

文献信息

• Construction of quaternary carbon centers by using substitution of γ,γ-disubstituted secondary allylic picolinates with alkylcopper reagents
  作者：Chao Feng、Yuki Kaneko、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2013.06.046

  日期：2013.8

  ZnI2 was found to promote regio- and stereoselective substitution of gamma,gamma-disubstituted secondary allylic picolinates with alkylcopper reagents derived from alkyl-MgBr and CuBr center dot Me2S in a 2:1 ratio to furnish quaternary carbon centers in good yields. Alkyl groups delivered efficiently were the primary, secondary, and benzyl classes such as Me, Et, Bu, C16H33, Ph(CH2)(2), Ph(CH2)(3), c-C6H11, and Bn. As an application, allylic picolinates with the (E)- or (Z)-olefin afforded quaternary carbon centers that are the enantiomers of each other. (C) 2013 Elsevier Ltd. All rights reserved.
• Allylic Substitution for Construction of a Chiral Quaternary Carbon Possessing an Aryl Group
  作者：Chao Feng、Yuichi Kobayashi

  DOI：10.1021/jo400248y

  日期：2013.4.19

  Phenylcopper reagents derived from 2:1 PhMgBr/Cu(acac)(2) and 3:1:1 PhMgBr/Cu(acac)(2)/ZnI2 were found to be highly reactive and regioselective in the allylic substitution of gamma,gamma-disubstituted secondary allylic picolinates designed for construction of a quaternary carbon, whereas the previous 2:1 ArMgBr/CuBr center dot Me2S reagent and that with ZnX2 were unsuccessful. The generality of the ArMgBr/Cu(acac)(2) reagent was examined with enantiomerically enriched allylic picolinates, which furnished quaternary carbons with high efficiency in >92% regioselectivity and >97% chirality transfer. Two cyclohexanes with a quaternary carbon were synthesized by using these reagents.
• Exploration of Aryllithium-Derived Copper Reagents for Quaternary-Stereogenic-Center-Forming Allylic Substitution of γ,γ-Disubstituted Secondary Allylic Picolinates
  作者：Yuichi Kobayashi、Takuri Ozaki

  DOI：10.1055/s-0035-1560907

  日期：——

  2-methyl-7-phenylhept-2-en-4-yl picolinate was reacted with phenyl copper reagents derived from phenyllithium with Cu(acac)2, Cu(OMe)2, CuBr·Me2S, and CuCN in 1–3:1 ratios in the presence of excess magnesium bromide. Although the SN2′ product with a quaternary carbon was formed, the regioselectivity was 90% at most. Instead, phenyllithium/copper(I) thiophene-2-carboxylate/magnesium bromide (Ph/Cu = 1.5–2:1, Mg/Li =

  用基于芳基锂的铜试剂对 γ,γ-二取代的仲烯丙基吡啶甲酸酯（2-PyCO2H 的酯）进行烯丙基取代以构建季碳。最初，2-methyl-7-phenylhept-2-en-4-yl picolinate 与衍生自苯基锂的苯基铜试剂在 1-3 中与 Cu(acac)2、Cu(OMe)2、CuBr·Me2S 和 CuCN 反应在存在过量溴化镁的情况下比例为 1。虽然形成了带有季碳的SN2'产物，但区域选择性最多为90%。相反，发现苯基锂/铜（I）噻吩-2-羧酸盐/溴化镁（Ph/Cu = 1.5–2:1，Mg/Li = >1）可产生 >98% 的区域选择性和足够的反应性。该系统成功地使用了八种芳基锂基铜试剂，这些试剂具有空间拥挤、给电子、或吸电子取代基。抗立体化学过程是通过使用对映体富集的香叶醛衍生的吡啶甲酸酯建立的。