{[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl]oxy}carbonylhydroxylamine | 217323-83-6

• 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-phenylethyl)cyclohexyl]oxy}carbonylhydroxylamine
• 英文别名: [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] N-hydroxycarbamate
• CAS: 217323-83-6
• 化学式: C₁₇H₂₅NO₃
• 分子量: 291.39
• InChiKey: IGVLBXRBQAHHSW-BPLDGKMQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 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-phenylethyl)cyclohexyl]oxy}carbonylhydroxylamine 在 三乙胺 、 calcium oxide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 2-O-ethyl 1-O-[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-acetylaziridine-1,2-dicarboxylate
  参考文献：
  名称：

  Reagent-controlled diastereoselective aminations with a new chiral nosyloxycarbamate

  摘要：

  The synthesis of a new chiral nosyloxycarbamate derived from Helmchen's auxiliary is described. Reactions performed with this aminating reagent successfully give the formation of diastereomeric allylic carbamates or diastereomeric aziridines starting from different kinds of olefins. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)00558-6
• 作为产物：
  描述：

  长叶薄荷酮 在 吡啶 、 copper(I) bromide 、 N,O-双三甲硅基羟胺 、 sodium 、 异丙醇 作用下， 反应 2.5h， 生成 {[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl]oxy}carbonylhydroxylamine
  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

• Reagent-controlled diastereoselective aminations with a new chiral nosyloxycarbamate
  作者：Stefania Fioravanti、Alberto Morreale、Lucio Pellacani、Paolo A. Tardella

  DOI：10.1016/s0040-4039(03)00558-6

  日期：2003.4

  The synthesis of a new chiral nosyloxycarbamate derived from Helmchen's auxiliary is described. Reactions performed with this aminating reagent successfully give the formation of diastereomeric allylic carbamates or diastereomeric aziridines starting from different kinds of olefins. (C) 2003 Elsevier Science Ltd. All rights reserved.
• 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.