(R)-(-)-3,7-dimethyl-3-(4-methoxyphenyl)octa-1,6-diene | 191212-50-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (R)-(-)-3,7-dimethyl-3-(4-methoxyphenyl)octa-1,6-diene
• 英文别名: (R)-sporochnol；(R)-1-(3,7-dimethylocta-1,6-dien-3-yl)-4-methoxybenzene；methoxy-sporochnol；1-[(3R)-3,7-dimethylocta-1,6-dien-3-yl]-4-methoxybenzene
• CAS: 191212-50-7
• 化学式: C₁₇H₂₄O
• 分子量: 244.377
• InChiKey: UNEJSLDWPMMUBG-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(-)-3,7-dimethyl-3-(4-methoxyphenyl)octa-1,6-diene 在 臭氧 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.17h， 以78%的产率得到(R)-2-(4-methoxyphenyl)-2-methylpentane-1,5-diol
  参考文献：
  名称：

  叔硼酸酯四元立体中心的对映选择性构建：方法和应用

  摘要：

  固定下来：一系列具有四元立体中心的多功能官能团的底物已经由叔硼酸酯制备，具有非常高的对映选择性（参见方案；Cb = N，N-二异丙基氨基甲酰基，pin = pinacolato）。还报道了具有连续季和叔立体中心的烯丙基硼酸酯的制备，以及在天然产物合成中的应用。

  DOI：

  10.1002/anie.201008067
• 作为产物：
  描述：

  3,7-二甲基-2,6-辛二烯-1-醇 在 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 copper acetylacetonate 、 四丙基高钌酸铵 、 titanium tetra-n-propoxide 、 二甲基硫 、 臭氧 、 N-甲基吗啉氧化物 、 间氯过氧苯甲酸 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 (R)-(-)-3,7-dimethyl-3-(4-methoxyphenyl)octa-1,6-diene
  参考文献：
  名称：

  Synthesis of (S)- and (R)-Sporochnol by Using the Allylic Substitution of the Secondary Allylic Picolinate

  摘要：

  The allylic substitution of secondary allylic picolinates and copper reagents for the construction of a quaternary carbon was applied to synthesis of sporochnol. The enantiomerically enriched allylic picolinate (R)-5 was synthesized through the asymmetric hydrogen transfer of acetylene ketone 11 and the Pd-catalyzed methylation of the iodoallylic alcohol 16a. The key allylic substitution of the allylic picolinate (R)-5 with 4-MeOC6H4MgBr/Cu(acac)(2) (2:1) proceeded with 95% chirality transfer with 98% regioselectivity to afford anti S(N)2' product 6 in 89% yield, which was converted to the methyl ether of unnatural (R)-sporochnol. Similarly, the methyl ether of (S)-sporochnol (the natural form) was synthesized.

  DOI：

  10.3987/com-15-s(t)11

文献信息

• Quaternary Carbon Stereogenic Centers through Copper-Catalyzed Enantioselective Allylic Substitutions with Readily Accessible Aryl- or Heteroaryllithium Reagents and Aluminum Chlorides
  作者：Fang Gao、Yunmi Lee、Kyoko Mandai、Amir H. Hoveyda

  DOI：10.1002/anie.201005124

  日期：2010.11.2

  of the notorious aryls is solved: The first efficient catalytic and enantioselective method for allylic substitutions that furnish quaternary carbon stereogenic centers by additions of aryl‐ or heteroarylmetals is reported (see scheme). Highly site‐ and enantioselective processes begin with readily available organolithium reagents.

  臭名昭著的芳基问题得到了解决：报道了第一个有效的催化和对映选择性烯丙基取代方法，通过添加芳基或杂芳基金属来提供季碳立构中心（参见方案）。高度位点和对映选择性过程始于容易获得的有机锂试剂。
• The absolute configuration of (+)-sporochnol A, the fish deterrent from the Caribbean marine alga Sporochnus bolleanus
  作者：Michiyasu Takahashi、Yoko Shioura、Taku Murakami、Kunio Ogasawara

  DOI：10.1016/s0957-4166(97)00119-5

  日期：1997.4

  The absolute configuration of (+)-sporochnol A, the fish deterrent from the Caribbean marine alga Sporochnus bolleanus, has been established as S based on the stereocontrolled synthesis of its (R)-(−)-enantiomer from (S)-epichlorohydrin.

  的绝对构型（+） - sporochnol A，从加勒比海藻鱼威慑Sporochnus bolleanus，已被确立为小号基于所述立体控制合成它的（- [R ）- （ - ） -对映体从（小号） -表氯醇。
• Total synthesis of (−)-sporochnol A, the fish deterrent, from a chiral malonate
  作者：Antoine Fadel、Lucie Vandromme

  DOI：10.1016/s0957-4166(99)00086-5

  日期：1999.3

  From a single chiron, the homochiral benzylic malonic acid ester (R)-(+)-2 available with high enantiomeric excess by enzymatic hydrolysis (PLE acetonic powder), enantiomerically pure (-)-sporochnol A 1 was prepared. This versatile method allows preparation of sporochnol 1, via aldehydes 7 and 15, in good overall yield. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of (S)- and (R)-Sporochnol by Using the Allylic Substitution of the Secondary Allylic Picolinate
  作者：Yuichi Kobayashi、Yusuke Sugihara、Toshifumi Tojo、Takuri Ozaki

  DOI：10.3987/com-15-s(t)11

  日期：——

  The allylic substitution of secondary allylic picolinates and copper reagents for the construction of a quaternary carbon was applied to synthesis of sporochnol. The enantiomerically enriched allylic picolinate (R)-5 was synthesized through the asymmetric hydrogen transfer of acetylene ketone 11 and the Pd-catalyzed methylation of the iodoallylic alcohol 16a. The key allylic substitution of the allylic picolinate (R)-5 with 4-MeOC6H4MgBr/Cu(acac)(2) (2:1) proceeded with 95% chirality transfer with 98% regioselectivity to afford anti S(N)2' product 6 in 89% yield, which was converted to the methyl ether of unnatural (R)-sporochnol. Similarly, the methyl ether of (S)-sporochnol (the natural form) was synthesized.
• Enantioselective Construction of Quaternary Stereogenic Centers from Tertiary Boronic Esters: Methodology and Applications
  作者：Ravindra P. Sonawane、Vishal Jheengut、Constantinos Rabalakos、Robin Larouche-Gauthier、Helen K. Scott、Varinder K. Aggarwal

  DOI：10.1002/anie.201008067

  日期：2011.4.11

  that bear versatile functional groups with quaternary stereogenic centers have been prepared with very high enantioselectivity from tertiary boronic esters (see scheme; Cb=N,N‐diisopropylcarbamoyl, pin=pinacolato). The preparation of allylboronic esters bearing contiguous quaternary and tertiary stereogenic centers, and applications to natural product synthesis are also reported.

  固定下来：一系列具有四元立体中心的多功能官能团的底物已经由叔硼酸酯制备，具有非常高的对映选择性（参见方案；Cb = N，N-二异丙基氨基甲酰基，pin = pinacolato）。还报道了具有连续季和叔立体中心的烯丙基硼酸酯的制备，以及在天然产物合成中的应用。