1-methoxybicyclo[2.2.2]oct-5-en-2-one | 38213-08-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-methoxybicyclo[2.2.2]oct-5-en-2-one
• CAS: 38213-08-0
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: OUYWPTDADVLKIK-UHFFFAOYSA-N

物化性质

• 沸点：
  234.1±28.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-methoxybicyclo[2.2.2]oct-5-en-2-one 以70%的产率得到
  参考文献：
  名称：

  ADCOCK, W.;ABEYWICKREMA, A. N., J. ORG. CHEM., 1982, 47, N 15, 2951-2957

  摘要：

  DOI：
• 作为产物：
  描述：

  6-chloro-6-cyano-1-methoxybicyclo<2.2.2>oct-2-ene 在 sodium sulfide 作用下， 以 乙醇 为溶剂， 反应 14.0h， 以50%的产率得到1-methoxybicyclo[2.2.2]oct-5-en-2-one
  参考文献：
  名称：

  Stereospecific skeletal rearrangement reactions in bridgehead-substituted bicyclo[2.2.2] systems under neutral conditions

  摘要：

  DOI：

  10.1021/jo00388a031

文献信息

• Perrhenic Acid-Catalyzed Dehydration from Primary Amides, Aldoximes,<i>N</i>-Monoacylureas, and α-Substituted Ketoximes to Nitrile Compounds
  作者：Yoshiro Furuya、Kazuaki Ishihara、Hisashi Yamamoto

  DOI：10.1246/bcsj.80.400

  日期：2007.1.15

  The dehydration reaction of primary amides is one of the most fundamental methods for the synthesis of nitriles, and the development of environmentally benign catalytic reaction processes is needed. We surveyed a variety of metal catalysts and found that perrhenic acid was extremely effective for the dehydration of not only primary amides but also aldoximes. Typically, 1 mol % of perrhenic acid gave

  伯酰胺的脱水反应是合成腈类最基本的方法之一，需要开发环境友好的催化反应工艺。我们调查了各种金属催化剂，发现高铼酸不仅对伯酰胺而且对醛肟的脱水都非常有效。通常，在共沸回流条件下，在甲苯或均三甲苯中除去水，1 mol%的高铼酸由酰胺或醛肟得到相应的腈。此外，高铼酸是一种非常有效的催化剂，用于将 α-取代的酮肟贝克曼裂解成官能化的腈。这种新的催化系统无需进一步修改即可应用于腈的克级合成。
• Evaluation of the π-conjugative effect of the 2-methylene and the 2-oxo substituent on the stability of carbocations in the solvolysis of bicyclic bridgehead derivatives
  作者：Ken'ichi Takeuchi、Fumio Akiyama、Keizo Ikai、Tadashi Shibata、Midori Kato

  DOI：10.1016/s0040-4039(00)82470-3

  日期：1988.1

  The incipient 2-methylenebicyclo[3.2.2]non-1-yl cation is stabilized by allylic conjugation by 4 kcal/mol compared with the more rigid 2-methylenebicyclo[2.2.2]oct-1-yl cation. In contrast to this, no appreciable stabilization due to carbonyl π-conjugation was detected in the 2-oxobicyclo[3.2.2]non-1-yl cation, indicating unimportance of π-conjugative stabilization in tertiary α-keto cations.

  与刚性较强的2-亚甲基双环[2.2.2]辛-1-基阳离子相比，初始的2-亚甲基双环[3.2.2]壬-1-基阳离子通过烯丙基结合稳定在4 kcal / mol。与此相反，在2-氧代双环[3.2.2]壬-1-基阳离子中未检测到由于羰基π-共轭引起的明显稳定，表明在叔α-酮基阳离子中π-共轭稳定的重要性不高。
• Rearrangement Approaches to Cyclic Skeletons. X. Pinacol-Type Rearrangement of 2-Substituted 1-Methoxybicyclo[2.2.2]oct-5-en-2-ols into Bicyclo[3.2.1]oct-6-en-2-ones. Remarkable Substituent Effects on Predominant Migration of the Unsaturated Bridge
  作者：Tadao Uyehara、Toshihiro Inayama、Toshiaki Furuta、Tadahiro Kato、Yoshinori Yamamoto、Masako Ueno、Toshio Sato

  DOI：10.1246/bcsj.69.1727

  日期：1996.6

  Pinacol-type rearrangement of 2-substituted 1-methoxybicyclo[2.2.2]oct-5-en-exo-2-ols (1) by treatment with p-toluenesulfonic acid in boiling benzene gave bicyclo[3.2.1]oct-6-en-2ones (2) and -3en-2-ones (4) in a ratio of ≥ 10 to 1 along with small amounts of dehydration products. Treatment of the endo isomers (3) under the same conditions gave 2, 4, and the dehydration products. The ratios of 2 to

  在沸腾苯中用对甲苯磺酸处理 2-取代的 1-甲氧基双环 [2.2.2]oct-5-en-exo-2-ols (1) 的频哪醇型重排得到双环 [3.2.1]oct-6 -en-2ones (2) 和 -3en-2-ones (4) 的比例≥ 10: 1 以及少量脱水产物。在相同条件下处理内异构体(3)得到2、4和脱水产物。在这种情况下，2 比 4 的比例在一定范围内，并受 C-2 位取代基的影响。1 的相对消失速率常数与相应的 3 的相对消失速率常数之比小于 10。这一观察结果表明不饱和桥在 1 的反应中没有提供显着的嵌合辅助。脱水产物的类似酸处理得到 2 和 4，它们的比例在某种程度上受取代基的影响。提出了频哪醇型重排的机制。
• Rearrangement Approaches to Cyclic Skeletons. IX. Stereoselective Total Synthesis of (±)-Camphorenone Based on a Ring-Contraction of Bicyclo[3.2.1]oct-6-en-2-one. Reliable One-Step Diazo Transfer Followed by a Wolff Rearrangement
  作者：Tadao Uyehara、Naohiko Takehara、Masako Ueno、Toshio Sato

  DOI：10.1246/bcsj.68.2687

  日期：1995.9

  onyl azide and potassium t-butoxide at −78 °C in THF. A Wolff rearrangement of the resulting α-diazoketones in the presence of water gave ring-contraction products, bicyclo[2.2.1]heptenecarboxylic acids. Using these two transformations the total synthesis of (±)-camphorenone was achieved stereoselectively, starting from 1-methoxybicyclo[2.2.2]oct-5-en-2-one.

  双环[3.2.1]oct-6-en-2-ones和相关化合物的直接重氮转移反应是通过在-78°C的THF中用2,4,6-三异丙基苯磺酰基叠氮化物和叔丁醇钾处理来完成的。在水的存在下，所得α-重氮酮的沃尔夫重排得到环收缩产物，双环[2.2.1]庚烯羧酸。使用这两个转化，从 1-甲氧基双环 [2.2.2] oct-5-en-2-one 开始，立体选择性地实现了 (±)-樟脑酮的全合成。
• Aspartic Protease Inhibitors
  申请人：Baldwin John J.

  公开号：US20100048636A1

  公开（公告）日：2010-02-25

  The present invention is directed to aspartic protease inhibitors. Certain aspartic protease inhibitors of the invention can be represented by the following structural formula or a pharmaceutically acceptable salt thereof. The present invention is also directed to pharmaceutical compositions comprising the disclosed aspartic protease inhibitors. The present invention is further directed to methods of antagonizing one or more aspartic proteases in a subject in need thereof, and methods for treating an aspartic protease mediated disorder in a subject using the disclosed aspartic protease inhibitors.

  本发明涉及天冬氨酸蛋白酶抑制剂。本发明所述的某些天冬氨酸蛋白酶抑制剂可以用以下结构式或其药学上可接受的盐来表示。本发明还涉及包括所述天冬氨酸蛋白酶抑制剂的药物组合物。本发明还涉及在需要拮抗一种或多种天冬氨酸蛋白酶的主体中的方法，以及使用所述天冬氨酸蛋白酶抑制剂治疗天冬氨酸蛋白酶介导的疾病的方法。