(-)-(1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-nitrophenyl)ethyl]cyclohexanol | 186045-26-1

• 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-nitrophenyl)ethyl]cyclohexanol
• 英文别名: (1R,2S,5R)-5-methyl-2-[2-(4-nitrophenyl)propan-2-yl]cyclohexan-1-ol
• CAS: 186045-26-1
• 化学式: C₁₆H₂₃NO₃
• 分子量: 277.364
• InChiKey: OZLYQXUFWLZQGX-KCPJHIHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-nitrophenyl)ethyl]cyclohexanol 在 三甲基氯化锡 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-nitrophenyl)ethyl]cyclohexyl (1R,6R)-bicyclo[4.2.0]octan-2-one-6-carboxylate
  参考文献：
  名称：

  手性环己烯酮羧酸酯与乙烯的[2 + 2]光环加成反应可高度非对映选择性地合成双环[4.2.0]辛烷酮衍生物

  摘要：

  含有（-）-8-（4-硝基苯基）薄荷基作为乙烯的手性助剂的环己烯酮羧酸酯的非对映选择性[2 + 2]光环加成反应产生的光环加合物是一种双环[4.2.0]辛酮衍生物，具有高度非对映选择性。在-78°C下在CH 2 Cl 2中进行的光反应产生了88％de的相应光环加合物。在存在Ti（OR）4或Me 3 SnCl的情况下，非对映选择性增加至高达92％de。

  DOI：

  10.1016/j.tetlet.2004.08.102
• 作为产物：
  描述：

  长叶薄荷酮 在 copper(l) iodide 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 (-)-(1R,2S,5R)-5-methyl-2-[1-methyl-1-(4-nitrophenyl)ethyl]cyclohexanol
  参考文献：
  名称：

  用于不对称自由基环化反应的手性助剂：应用于（+）-雷公藤酚的对映选择性合成。

  摘要：

  [图：见正文]由相同的手性来源（R）-普勒高尼制备的一系列差向异构的8-芳基薄荷基衍生物5a-d和6a-1被用作β-酮的不对称自由基环化反应中的手性助剂。由Mn（OAc）3介导的酯。手性前体8c和8d分别提供了环化产物10c和10d，为单一异构体（dr> 99：1），而前体9k的环化得到13k具有良好的立体选择性（dr = 24：1）。非对映异构体13e被用作90％ee中对（+）-雷公藤酚的对映选择性合成的关键中间体。

  DOI：

  10.1021/ol0068243

文献信息

• Tunable reactivity of geminal bis(silyl) enol derivatives leading to selective exo-IEDDA or Sakurai allylation with a β,γ-unsaturated ketoester
  作者：Zubao Gan、Zhiwen Chu、Jia Hu、Zhishan Su、Changwei Hu、Lu Gao、Zhenlei Song

  DOI：10.1039/c6cc04593f

  日期：——

  Two contrasting pathways in a SnCl₄-catalyzed reaction of geminal bis(silyl) enol derivatives with β,γ-unsaturated ketoesters have been achieved by tuning the R group in the enol moiety.

  通过调节烯醇部分中的R基团，实现了SnCl₄催化的双硅基烯醇衍生物与β,γ-不饱和酮酯反应中的两种对比途径。
• 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
• Chiral Auxiliaries for Asymmetric Radical Cyclization Reactions:  Application to the Enantioselective Synthesis of (+)-Triptocallol
  作者：Dan Yang、Ming Xu、Mai-Ying Bian

  DOI：10.1021/ol0068243

  日期：2001.1.1

  [figure: see text] A series of epimeric 8-aryl menthyl derivatives 5a-d and 6a-l, prepared from the same chiral source (R)-pulegone, were employed as chiral auxiliaries in the asymmetric radical cyclization reactions of beta-keto esters mediated by Mn(OAc)3. Chiral precursors 8c and 8d provided the cyclization products 10c and 10d, respectively, as single isomers (dr > 99:1), whereas the cyclization

  [图：见正文]由相同的手性来源（R）-普勒高尼制备的一系列差向异构的8-芳基薄荷基衍生物5a-d和6a-1被用作β-酮的不对称自由基环化反应中的手性助剂。由Mn（OAc）3介导的酯。手性前体8c和8d分别提供了环化产物10c和10d，为单一异构体（dr> 99：1），而前体9k的环化得到13k具有良好的立体选择性（dr = 24：1）。非对映异构体13e被用作90％ee中对（+）-雷公藤酚的对映选择性合成的关键中间体。
• Highly diastereoselective synthesis of bicyclo[4.2.0]octanone derivatives by the [2+2] photocycloaddition of chiral cyclohexenonecarboxylates to ethylene
  作者：Akinori Furutani、Ken Tsutsumi、Hiroaki Nakano、Tsumoru Morimoto、Kiyomi Kakiuchi

  DOI：10.1016/j.tetlet.2004.08.102

  日期：2004.10

  The diastereoselective [2+2] photocycloaddition of a cyclohexenonecarboxylate containing (−)-8-(4-nitrophenyl)menthyl as a chiral auxiliary to ethylene gave the photocycloadduct, a bicyclo[4.2.0]octanone derivative, with a high degree of diastereoselectivity. A photoreaction, conducted in CH2Cl2 at −78 °C gave the corresponding photocycloadduct in 88% de. In the presence of Ti(OR)4 or Me3SnCl, the

  含有（-）-8-（4-硝基苯基）薄荷基作为乙烯的手性助剂的环己烯酮羧酸酯的非对映选择性[2 + 2]光环加成反应产生的光环加合物是一种双环[4.2.0]辛酮衍生物，具有高度非对映选择性。在-78°C下在CH 2 Cl 2中进行的光反应产生了88％de的相应光环加合物。在存在Ti（OR）4或Me 3 SnCl的情况下，非对映选择性增加至高达92％de。