[2-(3,4-Dimethoxyphenyl)cyclohex-2-en-1-yl] methyl carbonate | 189364-06-5

• 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-(3,4-Dimethoxyphenyl)cyclohex-2-en-1-yl] methyl carbonate
• CAS: 189364-06-5
• 化学式: C₁₆H₂₀O₅
• 分子量: 292.332
• InChiKey: IAKJBNZUYYIZHV-UHFFFAOYSA-N

物化性质

• 沸点：
  428.6±45.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [2-(3,4-Dimethoxyphenyl)cyclohex-2-en-1-yl] methyl carbonate 在 palladium on activated charcoal 吡啶 、 咪唑 、 3,5-二甲基吡唑 、 chromium(VI) oxide 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三氟甲磺酸三甲基硅酯 、 RhCl(PPh₃)3 、 四丁基氟化铵 、 氢气 、 sodium naphthalenide 、 potassium carbonate 、 戴斯-马丁氧化剂 、 2,2'-双(二苯基氧膦)-1,1'-联萘 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 323.83h， 生成 松叶菊碱
  参考文献：
  名称：

  Total Syntheses of (−)-Mesembrane and (−)-Mesembrine via Palladium-Catalyzed Enantioselective Allylic Substitution and Zirconium-Promoted Cyclization

  摘要：

  4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp2ZrBu2, followed by treatment with MeMgBr and then O-2, gave 2a in 63% yield by a one-pot reaction, since the approach of Oz to zirconium was prevented by the aryl group. The total syntheses of (+/-)-mesembrane and (+/-)-mesembrine were achieved starting from 2a. To synthesize these natural products in a chiral form, the starting allylamine derivative 24 (80% yield, 86% ee, recrystallized from MeOH, 99% ee with 79% recovery) was prepared from allyl carbonate 22a and N-tosylallylamine 23 using palladium-catalyzed asymmetric amination in the presence of (S)-BINAPO as a chiral ligand. (-)-Mesembrane and (-)-mesembrine were synthesized from this allylamine 24.

  DOI：

  10.1021/jo9701187
• 作为产物：
  描述：

  2-bromocyclohex-2-en-1-ol 在 吡啶 、 四(三苯基膦)钯 、 双氧水 、 sodium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 5.3h， 生成 [2-(3,4-Dimethoxyphenyl)cyclohex-2-en-1-yl] methyl carbonate
  参考文献：
  名称：

  Total Syntheses of (−)-Mesembrane and (−)-Mesembrine via Palladium-Catalyzed Enantioselective Allylic Substitution and Zirconium-Promoted Cyclization

  摘要：

  4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp2ZrBu2, followed by treatment with MeMgBr and then O-2, gave 2a in 63% yield by a one-pot reaction, since the approach of Oz to zirconium was prevented by the aryl group. The total syntheses of (+/-)-mesembrane and (+/-)-mesembrine were achieved starting from 2a. To synthesize these natural products in a chiral form, the starting allylamine derivative 24 (80% yield, 86% ee, recrystallized from MeOH, 99% ee with 79% recovery) was prepared from allyl carbonate 22a and N-tosylallylamine 23 using palladium-catalyzed asymmetric amination in the presence of (S)-BINAPO as a chiral ligand. (-)-Mesembrane and (-)-mesembrine were synthesized from this allylamine 24.

  DOI：

  10.1021/jo9701187

文献信息

• Palladium-Catalyzed Asymmetric Allylic Substitution of 2-Arylcyclohexenol Derivatives:  Asymmetric Total Syntheses of (+)-Crinamine, (−)-Haemanthidine, and (+)-Pretazettine
  作者：Toyoki Nishimata、Yoshihiro Sato、Miwako Mori

  DOI：10.1021/jo030309b

  日期：2004.3.1

  Much interest has been shown in Amaryllidaceae alkaloids as synthetic targets due to their wide range of biological activities. Over 100 alkaloids have been isolated from members of the Amaryllidaceae family; most of them can be classified into eight skeletally homogeneous groups. We have succeeded in the first asymmetric total syntheses of the crinane-type alkaloids (+)-crinamine (1), (−)-haemanthidine

  由于金莲花科生物碱具有广泛的生物学活性，因此已显示出许多作为合成靶标的兴趣。从金莲花科的成员中已经分离出了100多种生物碱。它们中的大多数可以分为八个骨骼上同质的组。我们已经成功完成了首批不对称全合成的环戊烯型生物碱（+）-木胺（1），（-）-甘露定（2）和（+）-Pretazettine（3）。通过钯催化的不对称胺化从烯丙基膦酸酯11c获得起始环己烯基胺14，产率为82％，ee为74％。产物从MeOH中重结晶。有趣的是，（-）- 14从母液中得到ee含量为99％的ee（回收率为74％）。（-）- 10的分子内羰基-烯反应以高度立体选择性的方式进行，得到六氢吲哚衍生物9作为唯一产物。在路易斯酸催化的羰基烯反应中，以高收率分离出一种有趣的重排产物20。由9，合成（+）-木胺。因此，从11c开始，经过10个步骤完成了（+）-肉桂胺的不对称全合成，总收率为19％。通过短时间的步骤，也从9获得了（-）-甘露啶的总合成。
• Palladium-Catalyzed Allylic Substitution of Allyl Vinyl Carbonate
  作者：Miwako Mori、Toyoki Nishimata、Yuji Nagasawa、Yoshihiro Sato

  DOI：10.1002/1615-4169(20010129)343:1<34::aid-adsc34>3.0.co;2-9

  日期：2001.1.29

  effective leaving group in palladium-catalyzed allylic substitution. When the reaction of an equimolar amount of allyl methyl carbonate and allyl vinyl carbonate with dimethyl malonate was carried out in the presence of a palladium catalyst, allyl vinyl carbonate reacted with the nucleophile, and most of allyl methyl carbonate remained unchanged. In the reaction of a compound having allyl methyl carbonate

  发现碳酸乙烯基酯是钯催化的烯丙基取代中非常有效的离去基团。当在钯催化剂的存在下使等摩尔量的碳酸烯丙酯和碳酸烯丙酯与丙二酸二甲酯反应时，碳酸烯丙酯与亲核试剂反应，并且大部分碳酸烯丙酯保持不变。在分子中具有碳酸烯丙基甲基酯和碳酸烯丙基乙烯基酯的化合物与甲苯磺酰胺的反应中，在钯催化剂的存在下，亲核试剂与烯丙基碳酸乙烯基酯反应，并且碳酸烯丙基甲基酯保持不变。
• Palladium-catalyzed enantioselective synthesis of cyclohexene derivatives via kinetic resolution
  作者：Toyoki Nishimata、Kentaro Yamaguchi、Miwako Mori

  DOI：10.1016/s0040-4039(99)01079-5

  日期：1999.7

  Reaction of (+/-)-methyl 2-arylcyclohexenyl carbonate with tosyl amide in the presence of a catalytic amount of Pd(2)dba-CHCl3 and (S)-BINAPO produced 2-arylcyclohexenyl tosyl amide with a high ee along with the starting material with a high ee. The reaction involved two processes, and (+)- and (-)-methy] 2-arylcyclohexenyl carbonate gave the same (pi-allyl)palladium complex with a chiral ligand, which gave 2-arylcyclohexenyl tosyl amide with a high ee by enantioselective substitution. The intermediary (pi-allyl)palladium complex was synthesized, and the results of X-ray crystallography are shown. (C) 1999 Elsevier Science Ltd. All rights reserved.