(+)-8-(2-naphthyl)menthol | 211503-80-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (+)-8-(2-naphthyl)menthol
• 英文别名: (1S,2R,5S)-5-methyl-2-(2-naphthalen-2-ylpropan-2-yl)cyclohexan-1-ol
• CAS: 211503-80-9
• 化学式: C₂₀H₂₆O
• 分子量: 282.426
• InChiKey: AKVNKXYVBBUSEZ-JVPBZIDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+)-8-(2-naphthyl)menthol 在 platinum(IV) oxide 吡啶 、 草酰氯 、 N,O-双三甲硅基羟胺 、 氢气 、 二甲基亚砜 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 22.5h， 生成 (1S,4R,5R)-5-(6-Chloro-pyridin-3-yl)-2-oxa-3-aza-bicyclo[2.2.2]octane-3-carboxylic acid (1S,2R,5S)-5-methyl-2-(1-methyl-1-naphthalen-2-yl-ethyl)-cyclohexyl ester
  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
• 作为产物：
  描述：

  (-)-蒲勒酮 (S)-(-)-长叶薄荷酮 (S)-2-异亚丙基-5-甲基环己酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 copper(I) bromide 、 sodium 、 异丙醇 作用下， 生成 (+)-8-(2-naphthyl)menthol
  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

• Asymmetric total synthesis of (−)-epibatidine
  作者：Sakae Aoyagi、Ryuta Tanaka、Masaichi Naruse、Chihiro Kibayashi

  DOI：10.1016/s0040-4039(98)00803-x

  日期：1998.6

  An enantioselective approach to (−)-epibatidine based on asymmetric hetero Diels-Alder cycloaddition with an N-acylnitroso dienophile bearing 8-(2-naphthyl)menthol as a chiral source, wherein π-π stacking interaction between the naphthyl and nitrosocarbonyl groups may contribute to facial control, is described.

  对映体选择性方法，基于不对称杂Diels-Alder环加成反应，并带有N-酰基亚硝基双亲二烯体，带有8-（2-萘基）薄荷醇作为手性来源，其中萘基和亚硝基羰基之间的π-π堆积相互作用描述了有助于面部控制。
• Stereoselective dioxygenation of enoates
  作者：Patrick H. Dussault、Kevin R. Woller、Michael C. Hillier

  DOI：10.1016/s0040-4020(01)85363-1

  日期：1994.1
• Asymmetric Total Synthesis of (−)-Linderol A
  作者：Masayuki Yamashita、Navnath Dnyanoba Yadav、Takeshi Sawaki、Ikuko Takao、Ikuo Kawasaki、Yasuko Sugimoto、Akemi Miyatake、Kousuke Murai、Ayano Takahara、Ai Kurume、Shunsaku Ohta

  DOI：10.1021/jo070682+

  日期：2007.7.1

  The first asymmetric total synthesis of (-)-Linderol A, a potent inhibitor of melanin biosynthesis of cultured B-16 melanoma cells, has been achieved via two key reactions: a diastereoselective [2+2] photocycloaddition of a coumarin-3-carboxylate bearing a chiral auxiliary with 3-methyl-1-butene and a subsequent stereoconvergent transformation of the photoadducts with use of dimethylsulfoxonium methylide to afford a tetrahydrodibenzofuran derivative.