(3-methylhept-1-en-3-yl)benzene

• 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: (3-methylhept-1-en-3-yl)benzene
• 英文别名: 3-methyl-3-phenyl-1-heptene；3-Methylhept-1-en-3-ylbenzene；3-methylhept-1-en-3-ylbenzene
• 化学式: C₁₄H₂₀
• 分子量: 188.313
• InChiKey: ZYOABLZZAVERBI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  14
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  (E)-3-phenylbut-2-en-1-ol 在 copper(I) bromide dimethylsulfide complex 、 三溴化磷 、 (1R,7R)-4-{(S,S)-[bis(1-phenylethyl)]amino}-9,9-dimethyl-2,2,6,6-tetraphenyl-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decane 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (3-methylhept-1-en-3-yl)benzene
  参考文献：
  名称：

  第三和第四立体立体中心的对映选择性合成：铜/亚磷酰胺催化的有机锂试剂烯丙基烷基化

  摘要：

  报道了使用亚磷酰胺配体的伯和仲有机锂试剂对二取代的烯丙基卤进行高效且高度对映选择性的铜催化的烯丙基烷基化反应。三取代的烯丙基溴的使用首次允许使用这些反应性有机金属试剂对全碳四元立体异构中心进行对映选择性合成。

  DOI：

  10.1002/anie.201107840

文献信息

• Zirconium-mediated conversion of homoallylic ethers into cyclopropane derivatives
  作者：Vincent Gandon、Christophe Laroche、Jan Szymoniak

  DOI：10.1016/s0040-4039(03)01125-0

  日期：2003.6

  Homoallylic ethers react with Cp2ZrCl2/2 n-BuLi reagent to afford cyclopropane derivatives. Cyclopropylcarbinyl–homoallyl rearrangements involving zirconium species are observed depending on the substrate structure.

  高烯丙基醚与反应的Cp 2的ZrCl 2 /2 Ñ正丁基锂试剂，得到环丙烷衍生物。根据底物结构，观察到涉及锆物种的环丙基羰基-高烯丙基重排。
• Asymmetric Construction of Quaternary Stereogenic Centers via Auxiliary-Based SN2’ Reactions: A Case of 1,7-Relative Stereogenesis
  作者：Scott E. Denmark、Lyndon K. Marble

  DOI：10.3987/com-13-s(s)82

  日期：——

  The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with phenylcopper or n-butylcopper to provide alkenes in moderate to good yields and with moderate to high enantioselectivities at the newly created quaternary stereogenic center. The E-carbamate with methyl and cyclohexyl substituents at the gamma-terminus provided the highest yield (87%) and enantioselectivity (>99.9:0.1 er) of all the substitution patterns tested. The corresponding Z-carbamate gave the lowest enantioselectivity observed (80.0:20.0). Carbamates with other substituents (n-butyl and t-butyl) at the E-terminal position gave moderate yields and enantioselectivities of alkenes. Cinnamyl substrates also provided good yields of alkenes with moderate enantioselectivities. The origin of enantioselectivity is analyzed in the context of dimeric lithioheterocuprate structures.
• Grignard allylic substitution reaction catalyzed by 1,2,3-triazol-5-ylidene magnesium complexes
  作者：Ryosuke Nomura、Yuji Tsuchiya、Hiroyuki Ishikawa、Sentaro Okamoto

  DOI：10.1016/j.tetlet.2012.12.124

  日期：2013.3

  Allylic chlorides and phosphates reacted with alkyl-Grignard reagent in an S(N)2'-selective manner in the presence of a catalytic amount of 1,2,3-triazol-5-ylidenes to provide a-branched alkenes. (C) 2013 Elsevier Ltd. All rights reserved.
• Enantioselective Synthesis of Tertiary and Quaternary Stereogenic Centers: Copper/Phosphoramidite-Catalyzed Allylic Alkylation with Organolithium Reagents
  作者：Martín Fañanás-Mastral、Manuel Pérez、Pieter H. Bos、Alena Rudolph、Syuzanna R. Harutyunyan、Ben L. Feringa

  DOI：10.1002/anie.201107840

  日期：2012.2.20

  An efficient and highly enantioselective copper‐catalyzed allylic alkylation of disubstituted allyl halides with primary and secondary organolithium reagents using phosphoramidite ligands is reported. The use of trisubstituted allyl bromides allows, for the first time, the enantioselective synthesis of all‐carbon quaternary stereogenic centers with these reactive organometallic reagents.

  报道了使用亚磷酰胺配体的伯和仲有机锂试剂对二取代的烯丙基卤进行高效且高度对映选择性的铜催化的烯丙基烷基化反应。三取代的烯丙基溴的使用首次允许使用这些反应性有机金属试剂对全碳四元立体异构中心进行对映选择性合成。