(+/-)-Benzobicyclo<2.2.2>-octan-2-one | 74958-44-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (+/-)-Benzobicyclo<2.2.2>-octan-2-one
• 英文别名: (+/-)-(1R,8R)-tricyclo[6.2.2.0^2,7]dodeca-2,4,6-trien-9-one；2-Oxo-benzobicyclo-<2.2.2>-octen；(+/-)-benzobicyclo[2.2.2]octan-2-one；rac-(1R*,8R*)-tricyclo[6.2.2.0(2,7)]dodeca-2,4,6-trien-9-one；(1R,8R)-tricyclo[6.2.2.02,7]dodeca-2,4,6-trien-9-one
• CAS: 74958-44-4
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: JTAWEGXLKGECMT-LDYMZIIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-Benzobicyclo<2.2.2>-octan-2-one 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 正丁基锂 、 三乙胺 、 二异丙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 正庚烷 、 甲苯 为溶剂， 反应 10.0h， 生成 isobutyric acid (1S,8S,9S)-9-(2-{[3-(1H-benzoimidazol-2-yl)-propyl]-methyl-amino}-ethyl)-tricyclo[6.2.2.0^2,7]dodeca-2,4,6-trien-9-yl ester
  参考文献：
  名称：

  Discovery of novel bridged tetrahydronaphthalene derivatives as potent T/L-type calcium channel blockers

  摘要：

  Chemical evolution of mibefradil resulted in the identification of novel bridged tetrahydronaphthalene derivatives as potent T/L-type calcium channel blockers. A SAR study, in vitro and in vivo DMPK properties as well as the in vivo antihypertensive effect in rats are presented. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2015.07.038
• 作为产物：
  描述：

  三环(6.2.2.02,7)十二碳-4,9-二烯-3,6-二醇 在 吡啶 、 硼烷四氢呋喃络合物 、 戴斯-马丁氧化剂 、 三氯氧磷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 72.0h， 生成 (+/-)-Benzobicyclo<2.2.2>-octan-2-one
  参考文献：
  名称：

  Discovery of novel bridged tetrahydronaphthalene derivatives as potent T/L-type calcium channel blockers

  摘要：

  Chemical evolution of mibefradil resulted in the identification of novel bridged tetrahydronaphthalene derivatives as potent T/L-type calcium channel blockers. A SAR study, in vitro and in vivo DMPK properties as well as the in vivo antihypertensive effect in rats are presented. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2015.07.038

文献信息

• [EN] BRIDGED TETRAHYDRONAPHTHALENE DERIVATIVES<br/>[FR] DÉRIVÉS PONTÉS DU TÉTRAHYDRONAPHTALÈNE
  申请人：ACTELION PHARMACEUTICALS LTD

  公开号：WO2010046855A1

  公开（公告）日：2010-04-29

  The invention relates to compounds of formula (I) wherein R1, R2, R3, R4, A, B, W and n are as defined in the description, and to pharmaceutically acceptable salts of such compounds. These compounds are useful as calcium channel blockers.

  这项发明涉及式（I）的化合物，其中R1、R2、R3、R4、A、B、W和n如描述中所定义，并且涉及这些化合物的药用盐。这些化合物可用作钙通道阻滞剂。
• Diels-Alder reaction—IX
  作者：Ken'ichi Takeda、S. Hagishita、M. Sugiura、K. Kitahonoki、I. Ban、S. Miyazaki、K. Kuriyama

  DOI：10.1016/s0040-4020(01)92973-4

  日期：1970.1

  The Diels-Alder reaction of 1,7-, 2,7-, 2,6-, 1,6-dihydroxynaphthalene and 6-bromo-2-naphthol with maleic anhydride was investigated. All of these 2-naphthol derivatives gave exo- and endo-adducts (II and III) except for the bromo-naphthol, from which only endo-adduct was obtained. The assignment of exo or endo configuration was based on lactone formation on NaBH4 reduction possible only from the exo

  研究了1,7-，2,7-，2,6-，1,6-二羟基萘和6-溴-2-萘酚与马来酸酐的Diels-Alder反应。所有这些2-萘酚衍生物的给外-和内切-adducts（II和III），除了溴萘酚，其中只有内切得到-adduct。的分配外切或内切配置是基于上的NaBH内酯形成4减少可能只从外异构体，NMR谱的比较，并且在一些情况下，偶极矩的测量。形成的加合物的外/内比率在很宽的范围内变化。
• Asymmetric Hydrogenation of Bicyclic Ketones Catalyzed by BINAP/IPHAN−Ru(II) Complex
  作者：Noriyoshi Arai、Masaya Akashi、Satoshi Sugizaki、Hirohito Ooka、Tsutomu Inoue、Takeshi Ohkuma

  DOI：10.1021/ol101200z

  日期：2010.8.6

  chiral alcohols in 97−98% ee. 2-Diphenylmethyl-3-quinuclidinone was hydrogenated with the same catalyst to the cis alcohol with perfect diastereo- and enantioselectivity. The reaction of unsymmetrical ketones with a bicyclo[2.2.1] or -[2.2.2] skeleton gave the corresponding alcohols with high stereoselectivity.

  RuCl 2 [（S）-binap] [（R）-iphan]和t -C 4 H 9 OK的联合催化剂体系在2-中将3-quinuclidinone和双环[2.2.2] octan-2-one加氢丙醇可提供97-98％ee的手性醇。用相同的催化剂将2-二苯基甲基-3-奎宁环酮氢化成顺式醇，具有完美的非对映体和对映体选择性。不对称酮与双环[2.2.1]或-[2.2.2]骨架的反应得到了具有高立体选择性的相应醇。
• Atom- and Step-Economical Pathway to Chiral Benzobicyclo[2.2.2]octenones through Carbon-Carbon Bond Cleavage
  作者：Lantao Liu、Naoki Ishida、Masahiro Murakami

  DOI：10.1002/anie.201108446

  日期：2012.3.5

  nickel‐catalyzed asymmetric intramolecular alkene insertion reaction into cyclobutanones (1) has been developed. The reaction significantly reduces the number of steps required for the synthesis of chiral benzobicyclo[2.2.2]octenones (2).

  紧要关头：已经开发了镍催化的不对称分子内烯烃插入环丁酮的反应（1）。该反应显着减少了合成手性苯并双环[2.2.2]辛烯酮（2）所需的步骤数。
• Electronic Control of Stereoselectivity in the Metal Hydride Reductions of a Series of Substituted 3,4-Dihydro-1,4-ethanonaphthalen-2(1<i>H</i>)-ones
  作者：Keiji Okada、Seiji Tomita、Masaji Oda

  DOI：10.1246/bcsj.62.2342

  日期：1989.7

  The anti/syn stereoselectivity in the metal hydride reductions of a series of substituted 3,4-dihydro-1,4-ethanonaphthalen-2(1H)-ones was studied. The observed steroselectivity sequence was found to be parallel with the homoconjugation sequence except for the case of 5,8-dimethoxy-substituted derivative: the portion of anti attack increases as the benzene ring becomes electron-rich. The results were

  研究了一系列取代的 3,4-dihydro-1,4-ethonanaphthalen-2(1H)-ones 的金属氢化物还原中的反/syn 立体选择性。发现观察到的立体选择性序列与同共轭序列平行，除了 5,8-二甲氧基取代衍生物的情况：随着苯环变得富电子，抗攻击部分增加。结果被 Cieplak 的过渡态模型或非经典碳阳离子模型合理化。一种特殊的配位过渡态被认为可以解释 5,8-二甲氧基取代化合物的结果。