4,7,7,-三甲基二环[4.1.0]庚烷-3-甲醇 | 73494-49-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4,7,7,-三甲基二环[4.1.0]庚烷-3-甲醇
• 英文名称: (2R)-5-Phenyl-2-pentanol
• 英文别名: (R)-4-phenyl-2-pentanol；(R)-5-phenyl-2-pentanol；(R)-5-phenylpentan-2-ol；5-phenyl-2-pentanol；5-phenyl-2R-pentanol；(R)-alpha-Methylbenzenebutanol；(2R)-5-phenylpentan-2-ol
• CAS: 73494-49-2
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: ZFVFQRLBTBBQSK-SNVBAGLBSA-N

物化性质

• 沸点：
  110 °C(Press: 40 Torr)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  4,7,7,-三甲基二环[4.1.0]庚烷-3-甲醇 在 sodium hydroxide 、 四(三苯基膦)钯 、 正丁基锂 、 三苯基膦 、 zinc(II) chloride 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 19.5h， 生成 (S)-(-)-4-[4-methoxy-3-(5-phenylpent-2-yloxy)phenyl]benzoic acid
  参考文献：
  名称：

  Biarylcarboxylic Acids and -amides:  Inhibition of Phosphodiesterase Type IV versus [³H]Rolipram Binding Activity and Their Relationship to Emetic Behavior in the Ferret

  摘要：

  In addition to having desirable inhibitory effects on inflammation, anaphylaxis, and smooth muscle contraction, PDE-IV inhibitors also produce undesirable side effects including nausea and vomiting. In general, compounds that inhibit PDE-IV also potently displace [H-3]rolipram from a high-affinity binding site in rat cortex.(1,2) While this binding site has not been identified, it has been proposed to be an allosteric binding site on the PDE-IV enzyme.(3) Preliminary studies have suggested that the emetic potency of PDE-IV inhibitors is correlated with affinity for the brain rolipram binding site rather than potency at inhibiting PDE-IV enzyme activity. Efforts to eliminate the emetic potential of PDE-IV inhibitors were directed toward developing compounds with decreased [H-3]rolipram binding affinity while retaining PDE-IV potency. Thus, a novel series of 4-(3-alkoxy-4-methoxyphenyl)benzoic acids and their corresponding carboxamides were prepared and evaluated for their PDE-IV inhibitory and rolipram binding site properties. Modification of the catechol ether moiety led to phenylbutoxy and phenylpentoxy analogues that provided the desired actitivity profile. Specifically, 4-[3-(5-phenylpentoxy)-4-methoxyphenyl]-2-methylbenzoic acid, 18, was found to exhibit potent PDE-IV inhibitory activity (IC50 0.41 mu M) and possessed 400 times weaker activity than rolipram for the [H-3]rolipram binding site. In vivo, compound 18 was efficacious in the guinea pig aerosolized antigen induced airway obstruction assay (ED(50) 8.8 mg/kg, po) and demonstrated a significant reduction in emetic side effects (ferret, 20% emesis at 30 mg/kg, po).

  DOI：

  10.1021/jm9505066
• 作为产物：
  描述：

  (2S,3R,E)-5-phenylpent-4-ene-2,3-diol 在 palladium on activated charcoal lithium aluminium tetrahydride 、 氢气 、 Rochelle's salt 作用下， 以 乙醇 为溶剂， 25.0 ℃ 、405.3 kPa 条件下， 反应 4.0h， 生成 4,7,7,-三甲基二环[4.1.0]庚烷-3-甲醇
  参考文献：
  名称：

  Synthesis of the Enantiomeric Forms of 4-Hexanolide (γ-Caprolactone) from the Optically Active 5-Phenyl-4-pentene-2,3-diol Prepared from Cinnamaldehyde and Baker's Yeast

  摘要：

  DOI：

  10.1055/s-1980-28921
• 作为试剂：
  描述：

  (R)-(-)-α-methoxyphenylacetyl chloride 、 (S)-(+)-5-phenyl-2-pentanol 在 吡啶 、 4,7,7,-三甲基二环[4.1.0]庚烷-3-甲醇 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  使用在磷原子上带有伯烷基取代基的反式螯合手性全烷基双膦配体对酮进行不对称氢化硅烷化

  摘要：

  简单酮与二苯基硅烷的不对称氢化硅烷化在 -40 °C 下在铑配合物（0.001-0.01 摩尔量）存在下进行，该配合物与在磷原子上带有线性烷基取代基的反式螯合手性双膦配体（R，R） -(S,S)-Et-、Pr- 或 BuTRAP，得到相应的光学活性 (S)-仲醇，其 ee 高达 97%。使用具有更大 P 取代基的 TRAP 配体的不对称氢化硅烷化导致低得多的对映选择性。EtTRAP-铑催化剂对于具有铑原子配位位点的酮酯的不对称氢化硅烷化也有效（高达 98% ee）。通过使用 2.5 摩尔二苯基硅烷的不对称还原，从相应的二酮中获得了高达 99% ee 的旋光对称二醇。

  DOI：

  10.1246/bcsj.73.485

文献信息

• Catalyst-Controlled Diastereoselective Synthesis of Cyclic Amines via C-H Functionalization
  作者：Sailu Munnuri、Adeniyi Michael Adebesin、Mahesh P Paudyal、Muhammed Yousufuddin、Alfonso Dalipe、John R. Falck

  DOI：10.1021/jacs.7b09901

  日期：——

  restrictions, especially in complex molecule synthesis. This report describes a catalyst-controlled regio- and diastereoselective synthesis of N-unprotected pyrrolidines via dirhodium catalyzed intramolecular nitrene insertion into sp3 C-H bonds. The reaction proceeds at rt without external oxidants, nitrene stabilizing groups, or directing functionality. The insights that emerged from the conforma

  由于区分多个相对强的 sp3 CH 键的挑战，这些键的化学行为通常只有细微的差别，因此适用于非活化脂肪族系统的可靠区域和立体化学技术在很大程度上仍然难以捉摸。然而，使用导向基团和/或助剂的方法已经出现，但施加了实际限制，特别是在复杂分子合成中。本报告描述了一种催化剂控制的区域选择性和非对映选择性合成 N-未保护的吡咯烷，通过 dirhodium 催化分子内氮烯插入 sp3 CH 键。反应在室温下进行，无需外部氧化剂、氮烯稳定基团或导向官能团。
• Substituted dodecahydrotriphenylenes,
  申请人：Pfizer Inc.

  公开号：US04473704A1

  公开（公告）日：1984-09-25

  1,2,3,4,4a,4b,5,6,7,8,8a,12b-Dodecahydro-7-(oxo, hydroxy or amino)-9-hydroxy-11-(alkyl, alkoxy or alkoxyalkyl)triphenylenes, 2,3,3a,3b,4,5,6,7,7a,11b-decahydro-6-(oxo, hydroxy or amino)-8-hydroxy-10-(alkyl, alkoxy or alkoxyalkyl)-1H-cyclopenta[1]phenanthrenes, 2,3,4,4a,4b,5,6,7,8,8a-decahydro-7-(oxo, hydroxy or amino)-9-hydroxy-11-(alkyl, alkoxy, alkoxyalkyl, aralkyl, aralkoxy, aryloxyalkyl or aralkoxyalkyl)-1H-pyrido[1,2-f]phenanthridines, and 1,2,3,3a,3b,4,5,6,7,7a-decahydro-6-(oxo, hydroxy or amino)-8-hydroxy-10-(alkyl, alkoxy or alkoxyalkyl)pyrrolo[1,2-f]phenanthridines and derivatives are valuable as central nervous system active agents or as intermediates to compounds having such activity.

  1,2,3,4,4a,4b,5,6,7,8,8a,12b-十二氢-7-(氧代、羟基或氨基)-9-羟基-11-(烷基、烷氧基或烷氧基烷基)三苯基烯，2,3,3a,3b,4,5,6,7,7a,11b-十氢-6-(氧代、羟基或氨基)-8-羟基-10-(烷基、烷氧基或烷氧基烷基)-1H-环戊[1]菲，2,3,4,4a,4b,5,6,7,8,8a-十氢-7-(氧代、羟基或氨基)-9-羟基-11-(烷基、烷氧基、烷氧基烷基、芳烷基、芳烷氧基、芳氧基烷基或芳烷氧基烷基)-1H-吡啶并[1,2-f]菲啶，以及1,2,3,3a,3b,4,5,6,7,7a-十氢-6-(氧代、羟基或氨基)-8-羟基-10-(烷基、烷氧基或烷氧基烷基)吡咯并[1,2-f]菲啶及其衍生物，作为中枢神经系统活性剂或作为具有此类活性的化合物的中间体具有重要价值。
• The biogenic amine transporter activity of vinylogous amphetamine analogs
  作者：Ann M. Decker、John S. Partilla、Michael H. Baumann、Richard B. Rothman、Bruce E. Blough

  DOI：10.1039/c6md00245e

  日期：——

  A series of vinylogous amphetamine analogs was synthesized and examined for their activity at biogenic amine transporters and serotonin-2 receptor (5-HT2) subtypes. (1S,3E)-1-Methyl-4-phenyl-but-3-enylamine (S-6) is a potent dual dopamine/serotonin (DA/5-HT) releaser with no activity at 5-HT2 receptors. This unique profile of actions suggests that analog S-6 is a viable lead compound for identifying

  合成了一系列乙烯基苯丙胺类似物，并检查了它们对生物胺转运蛋白和血清素2受体（5-HT 2）亚型的活性。（1 S，3 E）-1-甲基-4-苯基-丁-3-烯胺（S - 6）是一种有效的多巴胺/ 5-羟色胺双重释放剂（DA / 5-HT），对5-HT 2受体没有活性。这种独特的作用表明，类似物S - 6是一种可行的先导化合物，可用于鉴定具有治疗益处和减少滥用风险的DA / 5-HT释放剂的新结构类别。
• Substituted hexahydropyrrolo[1,2-a]-quinolines, hexahydro-1H-pyrido[1,2-a]-
  申请人：Pfizer Inc.

  公开号：US04476131A1

  公开（公告）日：1984-10-09

  Tricyclic benzo fused compounds of the formula ##STR1## and pharmaceutically acceptable cationic and acid addition salts thereof, wherein n is zero, 1 or 2, and t is 1 or 2; M is CH or N, R.sub.1 is H or certain acyl groups; Q is CO.sub.2 R.sub.4, COR.sub.5, C(OR.sub.7)R.sub.5 R.sub.6, CN, CONR.sub.9 R.sub.10, CH.sub.2 NR.sub.9 R.sub.10, CH.sub.2 NHCOR.sub.11, CH.sub.2 NHSO.sub.2 R.sub.12, 5-tetrazolyl or when n is 1, Q and OR.sub.1 together form a lactone or certain reduced derivatives thereof; and Z is certain alkyl, alkoxy, alkoxyalkyl, aralkyl, aralkoxy, aryloxyalkyl or aralkoxyalkyl groups, are valuable central nervous system active agents, methods for their use, pharmaceutical compositions containing them and certain intermediates therefor.

  三环苯并化合物的结构式为##STR1##及其药学上可接受的阳离子和酸盐，其中n为零、1或2，t为1或2；M为CH或N，R.sub.1为H或特定的酰基；Q为CO.sub.2 R.sub.4、COR.sub.5、C(OR.sub.7)R.sub.5 R.sub.6、CN、CONR.sub.9 R.sub.10、CH.sub.2 NR.sub.9 R.sub.10、CH.sub.2 NHCOR.sub.11、CH.sub.2 NHSO.sub.2 R.sub.12、5-四唑基或当n为1时，Q和OR.sub.1共同形成内酯或其还原衍生物；Z为特定的烷基、烷氧基、烷氧基烷基、芳基烷基、芳基氧基、芳基氧基烷基或芳基烷氧基烷基基团，是有价值的中枢神经系统活性剂，其使用方法、含有它们的药物组合物以及某些中间体。
• Highly enantioselective hydrosilylation of simple ketones catalyzed by rhodium complexes of P-chiral diphosphine ligands bearing tert-butylmethylphosphino groups
  作者：Tsuneo Imamoto、Takuma Itoh、Yoshinori Yamanoi、Rintaro Narui、Kazuhiro Yoshida

  DOI：10.1016/j.tetasy.2006.02.008

  日期：2006.2

  P-Chiral diphosphine ligands, (S,S)-1,2-bis(tert-butylmethylphosphino)ethane [(S,S)-t-Bu-BisP∗], (R,R)-bis(tert-butylmethylphosphino)methane [(R,R)-t-Bu-MiniPHOS], and (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline [(R,R)-QuinoxP∗], were applied to the rhodium-catalyzed enantioselective hydrosilylation of simple ketones. The corresponding secondary alcohols were obtained in high yields with good

  P-手性二膦配体，（S，S）-1,2-双（叔丁基甲基膦基）乙烷[（S，S）-t -Bu-BisP ∗ ]，（R，R）-双（叔丁基甲基膦基）甲烷[（R，R）-t -Bu-MiniPHOS]和（R，R）-2,3-双（叔丁基甲基膦基）喹喔啉[（R，R）-QuinoxP ∗，被应用于铑催化的简单酮的对映选择性氢化硅烷化。以高收率获得相应的仲醇，其中良好至优异的对映体过量高达99％。