methyl (E)-2-benzyl-5-methylhex-2-enoate | 717103-00-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (E)-2-benzyl-5-methylhex-2-enoate
• 英文别名: (E)-2-benzyl-5-methyl-hex-2-enoic acid methyl ester
• CAS: 717103-00-9
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: KSQNSMSKQBQYRX-GXDHUFHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-羟基-5-甲基-2-亚甲基己酸甲酯 、 苯基三氟硼酸钾 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 作用下， 以 甲醇 、 甲苯 为溶剂， 以91%的产率得到methyl (E)-2-benzyl-5-methylhex-2-enoate
  参考文献：
  名称：

  铑催化Baylis–Hillman加合物形成的立体控制三取代烯烃

  摘要：

  据报道，通过铑催化未活化的Baylis-Hillman加合物与有机硼酸或三氟（有机）硼酸钾的反应，可形成立体定义的三取代烯烃的高效通用条件（参见方案）。

  DOI：

  10.1002/chem.200802276

文献信息

• Baylis–Hillman adducts in rhodium-catalyzed 1,4-additions: unusual reactivity
  作者：Laure Navarre、Sylvain Darses、Jean-Pierre Genet

  DOI：10.1039/b402928c

  日期：——

  In the presence of a rhodium catalyst, unactivated Baylis–Hillman adducts reacted with arylboronic acids to afford trisubstituted alkenes with good yields. This highly efficient reaction (aerobic conditions, low temperature) is believed to proceeds via an unexpected mechanism involving 1,4-addition/β-hydroxy elimination steps and not π-allyl type rhodium intermediates.

  在铑催化剂的作用下，未活化的 BaylisâHillman 加合物与芳基硼酸发生反应，生成三取代烯烃，且收率很高。这种高效反应（有氧条件、低温）被认为是通过一种意想不到的机制进行的，其中涉及 1,4-加成/δ-羟基消除步骤，而不是Ï-烯丙基型铑中间体。
• Access to Stereodefined Trisubstituted Alkenesvia Rhodium-Catalyzed 1,4-Addition of Potassium Trifluoro(organo)- borates to Baylis–Hillman Adducts
  作者：Laure Navarre、Sylvain Darses、Jean-Pierre Genet

  DOI：10.1002/adsc.200505336

  日期：2006.2

  In the presence of a rhodium catalyst, unactivated Baylis–Hillman adducts reacted regioselectively with potassium trifluoro(organo)borates to afford stereodefined trisubstituted alkenes with good yields. This highly efficient reaction (aerobic conditions, low temperature, absence of added phosphane ligand) is believed to proceed via a 1,4-addition/β-hydroxy elimination mechanism.

  在铑催化剂的存在下，未活化的Baylis-Hillman加合物与三氟（有机）硼酸钾区域选择性地反应，从而以良好的收率得到立体确定的三取代的烯烃。该高效反应（有氧条件，低温，不存在添加的膦配体）被认为是通过1，4-加成/β-羟基消除机理进行的。
• Rhodium Fluorapatite Catalyst for the Synthesis of Trisubstituted Olefins via Cross Coupling of Baylis−Hillman Adducts and Arylboronic Acids
  作者：M. Lakshmi Kantam、K. B. Shiva Kumar、B. Sreedhar

  DOI：10.1021/jo701982m

  日期：2008.1.1

  [GRAPHICS]For R-2 = CN, Z-isomer (99%) was obtained.Treatment of fluorapatite (prepared by incorporating basic species F- in apatite in situ by coprecipitation) with an aqueous solution of RhCl3 resulted in rhodium-exchanged fluorapatite catalyst (RhFAP), which successfully promoted cross coupling of Baylis-Hillman adducts with arylboronic acids to yield trisubstituted olefins. A variety of arylboronic acids and Baylis-Hillman adducts were converted to the corresponding trisubstituted olefins, demonstrating the versatility of the reaction. The reaction is highly stereoselective. RhFAP was recovered quantitatively by simple filtration and reused with almost consistent activity.
• Rhodium-Catalyzed Formation of Stereocontrolled Trisubstituted Alkenes from Baylis-Hillman Adducts
  作者：Thomas Gendrineau、Nicolas Demoulin、Laure Navarre、Jean-Pierre Genet、Sylvain Darses

  DOI：10.1002/chem.200802276

  日期：2009.4.27

  Efficient and general conditions for the formation of stereodefined trisubstituted alkenes by using the rhodium‐catalyzed reaction of unactivated Baylis–Hillman adducts with either organoboronic acids or potassium trifluoro(organo)borates are reported (see scheme).

  据报道，通过铑催化未活化的Baylis-Hillman加合物与有机硼酸或三氟（有机）硼酸钾的反应，可形成立体定义的三取代烯烃的高效通用条件（参见方案）。