(1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-bromophenyl)ethyl]cyclohexanol | 186045-25-0

• 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: (1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-bromophenyl)ethyl]cyclohexanol
• CAS: 186045-25-0
• 化学式: C₁₆H₂₃BrO
• 分子量: 311.262
• InChiKey: FBQOIZMBYXYLIA-KCPJHIHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-bromophenyl)ethyl]cyclohexanol 在 吡啶 、 盐酸 作用下， 以 四氢呋喃 为溶剂， 生成 4-Oxo-piperidine-1-carboxylic acid (1R,2S,5R)-2-[1-(4-bromo-phenyl)-1-methyl-ethyl]-5-methyl-cyclohexyl ester
  参考文献：
  名称：

  Lewis acid-promoted asymmetric conjugate allylation of N-acyl-2,3-dihydro-4-pyridones induced by intramolecular π interactions

  摘要：

  Lewis acid-promoted conjugate addition reaction of an allylsilane to a series of the chiral 8-arylmenthol-derived N-acyl-2,3-dihydro-4-pyridones leads to the 2-allyl-4-piperidones with moderate to high levels of asymmetric induction, indicating restacking contribution to chirality control. This methodology was applied to the asymmetric synthesis of (-)-N-methylconiine. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)02129-6
• 作为产物：
  描述：

  长叶薄荷酮 在 copper(I) bromide 、 溴 、 sodium 、 溶剂黄146 、 异丙醇 作用下， 以 四氯化碳 为溶剂， 反应 5.0h， 生成 (1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-bromophenyl)ethyl]cyclohexanol
  参考文献：
  名称：

  Total Synthesis of (−)-Epibatidine Using an Asymmetric Diels−Alder Reaction with a Chiral N-Acylnitroso Dienophile

  摘要：

  An asymmetric total synthesis of(-)-epibatidine (1), isolated from the skin of the Ecuadorian poison frog, Epipedobates tricolor, of the family Dendrobatidae, has been achieved by virtue of the development of asymmetric hetero Diels-Alder (D-A) cycloaddition with an N-acylnitroso dienophile bearing the optically active 8-arylmenthol as a chiral source. Thus, in situ oxidation of the hydroxamic acid ent-laf incorporating the (1S,2R,5S)-8-(2-naphthyl)menthyl auxiliary was performed using the Swern conditions to produce the acylnitroso dienophile, which reacted at once with 2-chloro-5-(1,5-cyclohexadienyl)pyridine (7) to provide the (1S,4R)-meta-aza cycloadduct 24 as a major diastereoisomer. The observed facial diastereoselectivity is consistent with a transition-state model with the naphthyl group in "stacked" position and with the acylnitroso group in the s-cis conformation, wherein pi attractive interaction between the naphthyl and nitrosocarbonyl groups may contribute to facial control. Compound 24 underwent hydrogenation followed by removal of the chiral auxiliary with LiH2NBH3 and reductive cleavage of the N-O bond with Mo(CO)(6) to give the amino alcohol derivative 29, which was converted to (-)-epibatidine via bromination followed by cyclization.

  DOI：

  10.1021/jo9813078

文献信息

• Total Synthesis of (−)-Epibatidine Using an Asymmetric Diels−Alder Reaction with a Chiral <i>N</i>-Acylnitroso Dienophile
  作者：Sakae Aoyagi、Ryuta Tanaka、Masaichi Naruse、Chihiro Kibayashi

  DOI：10.1021/jo9813078

  日期：1998.11.1

  An asymmetric total synthesis of(-)-epibatidine (1), isolated from the skin of the Ecuadorian poison frog, Epipedobates tricolor, of the family Dendrobatidae, has been achieved by virtue of the development of asymmetric hetero Diels-Alder (D-A) cycloaddition with an N-acylnitroso dienophile bearing the optically active 8-arylmenthol as a chiral source. Thus, in situ oxidation of the hydroxamic acid ent-laf incorporating the (1S,2R,5S)-8-(2-naphthyl)menthyl auxiliary was performed using the Swern conditions to produce the acylnitroso dienophile, which reacted at once with 2-chloro-5-(1,5-cyclohexadienyl)pyridine (7) to provide the (1S,4R)-meta-aza cycloadduct 24 as a major diastereoisomer. The observed facial diastereoselectivity is consistent with a transition-state model with the naphthyl group in "stacked" position and with the acylnitroso group in the s-cis conformation, wherein pi attractive interaction between the naphthyl and nitrosocarbonyl groups may contribute to facial control. Compound 24 underwent hydrogenation followed by removal of the chiral auxiliary with LiH2NBH3 and reductive cleavage of the N-O bond with Mo(CO)(6) to give the amino alcohol derivative 29, which was converted to (-)-epibatidine via bromination followed by cyclization.
• Lewis acid-promoted asymmetric conjugate allylation of N-acyl-2,3-dihydro-4-pyridones induced by intramolecular π interactions
  作者：Masayuki Sato、Sakae Aoyagi、Seiji Yago、Chihiro Kibayashi

  DOI：10.1016/s0040-4039(96)02129-6

  日期：1996.12

  Lewis acid-promoted conjugate addition reaction of an allylsilane to a series of the chiral 8-arylmenthol-derived N-acyl-2,3-dihydro-4-pyridones leads to the 2-allyl-4-piperidones with moderate to high levels of asymmetric induction, indicating restacking contribution to chirality control. This methodology was applied to the asymmetric synthesis of (-)-N-methylconiine. Copyright (C) 1996 Elsevier Science Ltd