d-fenchone | 119565-94-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: d-fenchone
• 英文别名: (1R)-1-Methylbicyclo<2.2.1>heptan-2-one；(R)-1-methylnorcamphor；(-)-(1R,4S)-1-methyl-2-norbornanone；(1R,4S)-1-methylbicyclo[2.2.1]heptan-2-one；(1R,4S)-1-Methyl-norcampher；1-Methyl-norcampher
• CAS: 119565-94-5
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: ZYVCBPCUGIGFJA-HTRCEHHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  d-fenchone 在 盐酸 、 N-溴代丁二酰亚胺(NBS) 、 lithium hydroxide monohydrate 、 FeSO₄.7H₂O 、 五氯化磷 、 氨 、 水 、 硝酸 、 N,N-二异丙基乙胺 、 Methanaminium,N-[(dimethylamino)(3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxy)methylene]-N-methyl-, hexafluorophosphate(1-) 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 、 乙腈 为溶剂， 反应 34.0h， 生成 (1S,3R)-methyl 3-(8-amino-1-bromoimidazo[1,5-a]pyrazin-3-yl)-1-methylcyclopentanecarboxylate
  参考文献：
  名称：

  [EN] BENZAMIDE IMIDAZOPYRAZINE BTK INHIBITORS
  [FR] COMPOSÉS BENZAMIDES ET IMIDAZOPYRAZINES UTILISÉS COMME INHIBITEURS DE LA BTK

  摘要：

  提供的是根据式I的布鲁顿酪氨酸激酶（Btk）抑制剂化合物、其药学上可接受的盐、含有它们的药物组合物或其在治疗中的用途。

  公开号：

  WO2016106623A1
• 作为产物：
  描述：

  (1S)-exo-2-Methylbicyclo<2.2.1>heptan-endo-2-ol 在 草酰氯 、 硫酸 、 水 、 二甲基亚砜 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 d-fenchone
  参考文献：
  名称：

  [EN] BENZAMIDE IMIDAZOPYRAZINE BTK INHIBITORS
  [FR] COMPOSÉS BENZAMIDES ET IMIDAZOPYRAZINES UTILISÉS COMME INHIBITEURS DE LA BTK

  摘要：

  提供的是根据式I的布鲁顿酪氨酸激酶（Btk）抑制剂化合物、其药学上可接受的盐、含有它们的药物组合物或其在治疗中的用途。

  公开号：

  WO2016106623A1

文献信息

• Influence of norbornanone substituents on both the Wagner–Meerwein skeletal rearrangements under sulfonation conditions and the diastereoselectivity of the corresponding N,N′-bis-fumaroyl sultams in uncatalyzed Diels–Alder cycloadditions to cyclopenta-1,3-diene
  作者：Anna Piątek、Christian Chapuis

  DOI：10.1016/j.tetlet.2013.05.147

  日期：2013.8

  is strongly influenced by the absence of a gem-dimethyl moiety at C(7). As a result, sulfonation at C(10) is less efficient due to a divergent pathway in the intermediate double bond formation and/or isomerization. Furthermore, the absence of such a gem-dimethyl moiety in the corresponding norbornane[10,2]sultam derivatives, sterically influences the orientation of the SO(1) and SO(2) substituents

  在磺化条件下，降冰片烷酮骨架的Wagner-Meerwein多米诺骨牌重排受到C（7）处不存在宝石-二甲基部分的强烈影响。结果，由于在中间双键形成和/或异构化中的发散途径，C（10）处的磺化效率较低。此外，在相应的降冰片烷[10,2] sultam衍生物中不存在这种宝石-二甲基部分会在空间上影响S O（1）和S O（2）取代基的取向，因此对π面空间屏蔽有影响热力学更稳定的抗-S-顺ñ-链烯酰基二亲糖。结果，在非螯合条件下，它们的非对映选择性[4 + 2]环加成到环戊-1,3-二烯上的效率不高，这是由于伪轴向S O（1）较少，并因此失去了伪C 2-对称性。 。
• Reaction Sequences Involving the Mutual Interconversion of All 10 Tertiary Dimethyl-2-norbornyl Cations. A Comparison of Predicted Products and Rates with Experiment
  作者：R. Haseltine、K. Ranganayakulu、N. Wong、T. S. Sorensen

  DOI：10.1139/v75-265

  日期：1975.7.1

  All 10 tertiary dimethyl-2-norbornyl cations have been prepared. There are sequences of individual steps which will in theory interconvert any given two of these cations, a total of 45 permutations. All of the possible sequences (within a defined limit on the allowable total number of steps) for performing these interconversions were determined using a digital computer. Each step used in the computer generated sequence had previously been assigned a trial activation free energy value and a comparison is made in this paper between the actual experimental rearrangement results (in terms of both the kinetics of disappearance for the cation and what product is in fact formed) and the predicted results.

  已制备了所有10种三级二甲基-2-去氢-去甲基环辛基阳离子。存在一系列单独步骤的序列，理论上可以相互转化这些阳离子中的任意两种，共45种排列组合。使用数字计算机确定了执行这些相互转化的所有可能序列（在允许的总步数限制内）。计算机生成的序列中使用的每个步骤都先前被分配了一个试验性活化自由能值，在本文中对实际实验重排结果（包括阳离子消失的动力学和实际形成的产物）与预测结果进行了比较。
• Rapid Access to Multisubstituted Acrylamides from Cyclic Ketones via Palladium/Norbornene Cooperative Catalysis
  作者：Zhao Wu、Guangbin Dong

  DOI：10.1002/anie.202201239

  日期：2022.4.19

  A palladium/norbornene-catalyzed vicinal difunctionalization of enol triflates has been developed for rapid, modular and regioselective synthesis of multisubstituted acrylamides from simple ketones. The reaction exhibits broad functional group tolerance, and the use of bulky secondary amide-derived norbornenes appears to be a key parameter to maintain high efficiency and selectivity.

  已经开发了钯/降冰片烯催化的烯醇三氟甲磺酸酯的邻位双官能化，用于从简单的酮快速、模块化和区域选择性地合成多取代丙烯酰胺。该反应具有广泛的官能团耐受性，使用大体积仲酰胺衍生的降冰片烯似乎是保持高效率和选择性的关键参数。
• Benzamide imidazopyrazine Btk inhibitors
  申请人：MERCK SHARP & DOHME CORP.

  公开号：US10087188B2

  公开（公告）日：2018-10-02

  The present invention provides Bruton's Tyrosine Kinase (Btk) inhibitor compounds according to Formula (I), or pharmaceutically acceptable salts thereof, or to pharmaceutical compositions comprising these compounds and to their use in therapy. In particular, the present invention relates to the use of Btk inhibitor compounds of Formula (I) in the treatment of Btk mediated disorders.

  本发明提供了根据式（I）的布鲁顿酪氨酸激酶（Btk）抑制剂化合物或其药学上可接受的盐，或包含这些化合物的药物组合物及其在治疗中的用途。特别是，本发明涉及式（I）的 Btk 抑制剂化合物在治疗 Btk 介导的疾病中的用途。
• Chiral Synthesis via Organoboranes. 42. Selective Reductions. 57. Efficient Kinetic Resolution of Representative α-Tertiary Ketones with <i>B</i>-Chlorodiisopinocampheylborane
  作者：P. Veeraraghavan Ramachandran、Guang-Ming Chen、Herbert C. Brown

  DOI：10.1021/jo951206z

  日期：1996.1.1

  Kinetic resolution of racemic alpha-tertiary ketones with 0.5-0.6 molar equiv of B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric and enantiomeric excess, with the unreacted ketone recovered in very high ee. For example, ethyl 1-methyl-8-oxocyclopentane- and -cyclohexanecarboxylates are partially reduced to recover the ketone in 91 greater than or equal to 99% ee and the product alcohols in up to 94% de, with >90% ee for the major diastereomer. Bicyclic ketones, such as 1-methyl- and 1-ethylnorcamphor, camphor, and camphenilone, are readily resolved to provide the ketone in 92 to greater than or equal to 99% ee, with the product alcohol recovered in high de and ee. Dihydrospiro[bicyclo[3.2.1]octane-2,2'(3'H)-furan]-3-one is resolved to provide the ketone in greater than or equal to 99% ee and the product alcohol in greater than or equal to 99% de. In all the cases studied, the R-isomer of the ketone is recovered when (d)Ipc(2)BCl is used for kinetic resolution, while (l)Ipc(2)BCl provides the S-ketone. Optimum conditions for obtaining the product alcohol, or the ketone, or both, in very high yields and ee have been established.