(4S)-3-exo-(1-naphthyl)-4,7,7-trimethylbicyclo[2.2.1]heptan-2-exo-ol | 86835-18-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (4S)-3-exo-(1-naphthyl)-4,7,7-trimethylbicyclo[2.2.1]heptan-2-exo-ol
• 英文别名: (1S,2R,3R,4S)-4,7,7-trimethyl-3-naphthalen-1-ylbicyclo[2.2.1]heptan-2-ol
• CAS: 86835-18-9
• 化学式: C₂₀H₂₄O
• 分子量: 280.41
• InChiKey: QWJIWXOLJZRJMC-MLYOOKFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• 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：

  (4S)-3-exo-(1-naphthyl)-4,7,7-trimethylbicyclo[2.2.1]heptan-2-exo-ol 在 dirhodium tetraacetate 、 正丁基锂 、 对甲苯磺酰叠氮 、 sodium hydride 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 (1S,5R)-2-Oxo-5-phenyl-cyclopentanecarboxylic acid (1S,2R,3R,4S)-4,7,7-trimethyl-3-naphthalen-1-yl-bicyclo[2.2.1]hept-2-yl ester
  参考文献：
  名称：

  Enantioselective carbocyclization: a facile route to chiral cyclopentanes

  摘要：

  DOI：

  10.1021/ja00356a048
• 作为产物：
  描述：

  (3-endo-hydroxy-2-exo-naphthyl)bornane 在 lithium aluminium tetrahydride 、 pyridinium chlorochromate 作用下， 生成 (4S)-3-exo-(1-naphthyl)-4,7,7-trimethylbicyclo[2.2.1]heptan-2-exo-ol
  参考文献：
  名称：

  Enantioselective carbocyclization: a facile route to chiral cyclopentanes

  摘要：

  DOI：

  10.1021/ja00356a048

文献信息

• Stereoselective Reduction of<i>β</i>,<i>δ</i>-Diketo Esters. A Novel Strategy for the Synthesis of Artificial HMG-CoA Reductase Inhibitors
  作者：Tamejiro Hiyama、Guntoori Bhaskar Reddy、Tatsuya Minami、Takeshi Hanamoto

  DOI：10.1246/bcsj.68.350

  日期：1995.1

  Condensation of N-methoxy-N-methyl amides with the dianions of acetoacetates gives in good yields β,δ-diketo esters, which are reduced with Et2BOMe–NaBH4 in tetrahydrofuran–methanol highly selectively to give syn-β,δ-dihydroxy esters in one step. Similarly, the β,δ-diketo esters of the Taber’s chiral alcohol or its enantiomer respectively are reduced to give syn-β,δ-dihydroxy esters of moderate enantiomeric excess. Higher diastereo- and enantioselectivity were achieved by reduction of the β,δ-diketo esters of the Taber’s chiral alcohol or its enantiomer successively with diisobutylalane and with Et2BOMe–NaBH4. The resulting syn-diol esters were hydrolyzed and lactonized to give various types of β-hydroxy-δ-lactones commonly found in artificial HMG-CoA reductase inhibitors.

  N-甲氧基-N-甲基酰胺与乙酰乙酸酯的二阴离子缩合，高产率地得到了β，δ-二酮酯，这些二酮酯在四氢呋喃-甲醇中与Et2BOMe-NaBH4还原，高度选择性地一步得到syn-β，δ-二羟基酯。类似地，Taber的手性醇或其对映体的β，δ-二酮酯分别还原得到中等对映体纯度的syn-β,δ-二羟基酯。通过先后使用二异丁基铝烷和Et2BOMe-NaBH4还原Taber的手性醇或其对映体的β,δ-二酮酯，获得了更高的非对映选择性和对映选择性。得到的syn-二醇酯经水解和内酯化得到多种常见于人工HMG-CoA还原酶抑制剂中的β-羟基-δ-内酯。
• General [4 + 1] Cyclization Approach To Access 2,2-Disubstituted Tetrahydrofurans Enabled by Electrophilic Bifunctional Peroxides
  作者：Min Gao、Yukun Zhao、Chen Zhong、Shengshu Liu、Pengkang Liu、Qi Yin、Lin Hu

  DOI：10.1021/acs.orglett.9b02012

  日期：2019.7.19

  function as unique electrophilic oxygen synthons, for the synthesis of a broad range of 2,2-disubstituted tetrahydrofurans is achieved under operationally simple conditions. The unprecedented asymmetric version of such reaction is also realized via chiral auxiliary-assisted cyclization, thus providing a distinct approach to access chiral tetrahydrofurans with high diastereoselectivities. The new method

  羰基亲核体与2-碘甲基烯丙基过氧化物的一般[4 +1]环化反应可在操作简单的条件下完成，该过氧化物用作独特的亲电子氧合成子，可合成范围广泛的2，2-二取代的四氢呋喃。这种反应的前所未有的不对称形式也可以通过手性辅助环化来实现，从而提供了一种独特的方法来获得具有高非对映选择性的手性四氢呋喃。该新方法可用于泊沙康唑药物核心结构的合成。
• Enantioselective construction of dialkylcarbinols: synthesis of (-)-5-hexadecanolide
  作者：Douglass F. Taber、P. Bruce Deker、Micheal D. Gaul

  DOI：10.1021/ja00258a039

  日期：1987.11

  bornanaryle-2 de β-oxacides en hydroxyacides diastereoisomeres par Zn(BH 4 ) 2 /ZnCl 2 ou par le DIBAL/BHT; transformation d'un des hydroxyesters obtenus, l'hydroxy-3 myristate de [naphtyl-1]-3 bornanyle-2 en (−)-undecyl-6 perhydro pyranonne-2

  [naphtyl-1]-3 Bornanaryle-2 de β-oxacides en hydroxyacides 非对映异构体 Zn(BH 4 ) 2 /ZnCl 2 ou par le DIBAL/BHT 的还原练习曲；转化 d'un des hydroxyesters obtenus, l'hydroxy-3 myristate de [naphtyl-1]-3 Bornanyle-2 en (-)-undecyl-6 perhydro pyranonne-2
• Optically active esters of 7-substituted 3,5-difunctionalized
  申请人：Sagami Chemical Research Center

  公开号：US05276154A1

  公开（公告）日：1994-01-04

  The present invention provides optically active esters of 7-substituted 3,5-difunctionalized 6-heptenoic acids represented by the following formula: ##STR1## wherein R is a substituted or unsubstituted aromatic group, a substituted or unsubstituted heteroaromatic group or a substituted vinyl group; Ar is a condensed aromatic group; X.sup.1 and Y.sup.1 are not the same and each is a hydrogen atom or a hydroxyl group, or may be combined to represent an oxygen atom which forms a carbonyl group together with the carbon atom to which X.sup.1 and Y.sup.1 are attached; and X.sup.2 and Y.sup.2 are not the same and each is a hydrogen atom or a hydroxyl group, or may be combined to represent an oxygen atom which forms a carbonyl group together with the carbon atom to which X.sup.2 and Y.sup.2 are attached, or enantiomers thereof. The present invention further provides processes for preparing the above optically active esters and 7-substituted (3R, 5S, 6E)-3,5-dihydroxy-6-hepten-1,5-olides. These esters are useful as synthetic intermediates for preparing the above lactones having an inhibitory activity of HMG-CoA reductase as well as a sex attractant pheromone of beetles, endo-1,3-dimethyl-2,9-dioxabicyclo[3.3.1]nonane.

  本发明提供了以下式子所示的7-取代3,5-二官能团6-庚烯酸的光学活性酯：##STR1## 其中R是取代或未取代的芳基、取代或未取代的杂环芳基或取代的乙烯基；Ar是缩合芳基；X1和Y1不相同，每个都是氢原子或羟基，或者可以结合在一起表示氧原子，与X1和Y1连接的碳原子形成羰基；X2和Y2不相同，每个都是氢原子或羟基，或者可以结合在一起表示氧原子，与X2和Y2连接的碳原子形成羰基，或其对映体。本发明还提供了制备上述光学活性酯和7-取代（3R，5S，6E）-3,5-二羟基-6-庚烯-1,5-内酯的方法。这些酯可用作合成中间体，用于制备具有HMG-CoA还原酶抑制活性以及甲虫的性引诱素内-1,3-二甲基-2,9-二氧杂双环[3.3.1]壬烷的上述内酯。
• The Rh2(OAc)4 catalysed CH insertion in chiral ester diazoanilides
  作者：Andrew G.H. Wee、Baosheng Liu

  DOI：10.1016/0040-4039(95)02115-9

  日期：1996.1

  The Rh2(OAc)4 -catalysed CH insertion reaction in chiral ester diazoanilides was investigated and was found to yield 4-substituted 2-pyrrolidinones with moderate to high e.e. (37–98 %) after decarbalkoxylation. Electronic effects were found to oppose steric effects in influencing the enantioselectivity of the reaction in N-arylethyl diazoanilides.

  研究了Rh 2（OAc）4催化的手性酯重氮苯胺化物中的CH插入反应，发现该化合物在脱碳烷氧基化后可产生具有中等至较高ee（37-98％）的4-取代的2-吡咯烷酮。发现在影响N-芳基乙基重氮苯胺中反应的对映选择性方面，电子效应与空间效应相反。