exo-2-bromobicyclo<2.2.1>heptane-1-carboxylic acid | 2534-90-9

• 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: exo-2-bromobicyclo<2.2.1>heptane-1-carboxylic acid
• 英文别名: (+/-)-2-exo-bromonorbornane-1-carboxylic acid；exo-2-bromonorbornane-1-carboxylic acid；2exo-Brom-norbornancarbonsaeure；(+/-)-2exo-bromo-norbornane-1-carboxylic acid；(+/-)-2exo-Brom-norbornan-1-carbonsaeure；2-exo-Brom-bicyclo<2.2.1>heptan-1-carbonsaeure；Rel-(1R,2R,4S)-2-bromobicyclo[2.2.1]heptane-1-carboxylic acid；(1R,2R,4S)-2-bromobicyclo[2.2.1]heptane-1-carboxylic acid
• CAS: 2534-90-9；74830-47-0；85173-61-1；104085-10-1；104113-37-3；104113-38-4
• 化学式: C₈H₁₁BrO₂
• 分子量: 219.078
• InChiKey: YOBWYLCYNUIVKF-JKMUOGBPSA-N

物化性质

• 沸点：
  314.1±25.0 °C(Predicted)
• 密度：
  1.730±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  exo-2-bromobicyclo<2.2.1>heptane-1-carboxylic acid 在 sodium hydroxide 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 氯化亚砜 、 硫酸 、 三甲基氯化锡 、 tripropylammonium fluorochromate (VI) 、 溶剂黄146 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 13.75h， 生成 bicyclo<2.2.2>octane-1-carboxaldehyde tosylhydrazone
  参考文献：
  名称：

  Bicyclo[3.2.2]non-1-ene: matrix isolation and spectroscopic characterization of a moderately strained bridgehead olefin

  摘要：

  Bicyclo[3.2.2]non-1-ene was generated in low-temperature matrices and in fluid solutions by photodecomposition of bicyclo[2.2.2]oct-1-yldiazomethane and its photorearrangement product, 3-(bicyclo[2.2.2]oct-1-yl)diazirine. It was characterized by IR and UV absorption and by H-1 and C-13 NMR spectroscopy. Further evidence for the proposed structure was provided by self-trapping and by the spectral effects of deuteration on the olefinic carbon. Observed IR spectra and isotopic shifts agree well with the results of semiempirical (MNDO) and ab initio (SCF/6-31G*) calculations.

  DOI：

  10.1021/jo00066a018
• 作为产物：
  描述：

  (+/-)-2-bromo-norbornane-2endo-carboxylic acid 生成 exo-2-bromobicyclo<2.2.1>heptane-1-carboxylic acid
  参考文献：
  名称：

  β-Bromo Acids. II. Solvolysis of Cyclic β-Bromo Acids^1-3

  摘要：

  DOI：

  10.1021/ja01088a020

文献信息

• Synthese einiger 1,2-Dihalogen-norbornane
  作者：Ernst-Peter Krebs、Reinhart Keese

  DOI：10.1002/hlca.19820650710

  日期：1982.11.3

  Synthesis of some 1,2-Dihalogenonorbornanes

  一些1,2-二卤代降冰片烷的合成
• From norbornane-based nucleotide analogs locked in South conformation to novel inhibitors of feline herpes virus
  作者：Milan Dejmek、Hubert Hřebabecký、Michal Šála、Martin Dračínský、Eliška Procházková、Pieter Leyssen、Johan Neyts、Jan Balzarini、Radim Nencka

  DOI：10.1016/j.bmc.2014.04.004

  日期：2014.6

  A synthetic route toward a series of unique cyclic nucleoside phosphonates locked in South conformation is described. The desired conformation is stabilized by a substitution of the sugar moiety by bicyclo[2.2.1]heptane (norbornane) bearing a purine or pyrimidine nucleobase in the bridgehead position. Although the final phosphonate derivatives are devoid of any significant antiviral activity probably

  描述了合成路线的一系列独特的环状核苷膦酸酯锁定在南构象。通过在桥头位置带有嘌呤或嘧啶核碱基的双环[2.2.1]庚烷（降冰片烷）取代糖部分，可以稳定所需的构象。尽管最终的膦酸酯衍生物可能由于不利的构象特性而没有任何重要的抗病毒活性，但一些中间体及其类似物对猫疱疹病毒显示出令人惊讶的活性。由于这些化合物不具有适当的羟甲基官能团，因此无法进行磷酸化并随后掺入多核苷酸链中，这些化合物似乎是通过一种未知的新作用机制起作用，并可能代表这种广泛传播的猫感染的核苷和核苷酸治疗药物的新的可能替代品。许多衍生物还对柯萨奇病毒B3和B4发挥了重要的抗病毒活性。
• The rearrangement of exo-2-bromobicyclo[2,2,1]heptane-1-carboxylic acid during reduction with lithium aluminium hydride
  作者：J. MacMillan、R. J. Pryce

  DOI：10.1039/j39710001818

  日期：——

  Contrary to a previous report, endo-2-hydroxymethylbicyclo[2,2,1]heptane is not the only product of reduction with lithium aluminium hydride of exo-2-bromobicyclo[2,2,1]heptane-1-carboxylic acid. The reduction product has been identified as a mixture of endo- and exo-2-hydroxymethylbicyclo[2,2,1]heptane and 1-hydroxymethylbicyclo[2,2,1]heptane. Evidence for the common intermediacy of exo-2-bromo-1

  相反，以前的报告中，内切-2- hydroxymethylbicyclo [2,2,1]庚烷不降低用氢化铝锂的唯一的产品外切-2-溴双环[2,2,1]庚烷-1-羧酸。还原产物已被鉴定为内-和外-2-羟甲基双环[2,2,1]庚烷和1-羟甲基双环[2,2,1]庚烷的混合物。提出了关于exo -2-bromo-1-hydroxymethylbicyclo [2,2,1]庚烷的常见中间证据。
• Absolute configuration of (+)-2-exo-bromonorbornane 1-carboxylic acid and (–)-1-iodo-2-exo-bromonorbornane
  作者：Susanna Müller、Reinhart Keese、Peter Engel、Günther Snatzke

  DOI：10.1039/c39860000297

  日期：——

  Resolution of (±)-2-exo-bromonorbornane-1-carboxylic acid was achieved by h.p.l.c. separation of diastereoisomeric amides, obtained from this acid and (+)-(R)-phenylglycinol; the absolute configuration was established by X-ray structure analysis and correlated with c.d. spectra.

  通过（HPLC）分离由该酸和（+）-（R）-苯基甘氨醇制得的非对映异构酰胺，可实现（±）-2-外-溴-降冰片烷-1-羧酸的拆分。通过X射线结构分析确定绝对构型并与cd光谱相关。
• Palladium/Norbornene‐Catalyzed Direct Vicinal Di‐Carbo‐Functionalization of Indoles: Reaction Development and Mechanistic Study
  作者：Xin Liu、Yun Zhou、Xiaotian Qi、Renhe Li、Peng Liu、Guangbin Dong

  DOI：10.1002/anie.202310697

  日期：2023.10.23

  Methods that can simultaneously install multiple different functional groups to heteroarenes via C−H functionalizations are valuable for complex molecule synthesis, which, however, remain challenging to realize. Here we report the development of vicinal di‐carbo‐functionalization of indoles in a site‐ and regioselective manner, enabled by the palladium/norbornene (Pd/NBE) cooperative catalysis. The reaction is initiated by the Pd(II)‐mediated C3‐metalation and specifically promoted by the C1‐substituted NBEs. The mild, scalable, and robust reaction conditions allow for a good substrate scope and excellent functional group tolerance. The resulting C2‐arylated C3‐alkenylated indoles can be converted to diverse synthetically useful scaffolds. The combined experimental and computational mechanistic study reveals the unique role of the C1‐substituted NBE in accelerating the turnover‐limiting oxidative addition step.

  摘要能够通过 C-H 功能化同时在杂环烯上安装多个不同官能团的方法对于复杂分子的合成非常有价值，然而实现这种方法仍然具有挑战性。在此，我们报告了通过钯/降冰片烯（Pd/NBE）协同催化，以位点选择性和区域选择性的方式对吲哚进行邻位二羧基官能化的研究进展。反应由 Pd(II) 介导的 C3 金属化引发，并由 C1 取代的 NBE 特别促进。反应条件温和、可扩展且稳健，因而具有良好的底物范围和优异的官能团耐受性。生成的 C2 芳基化 C3 烯基吲哚可转化为多种有用的合成支架。实验和计算机理的综合研究揭示了 C1 取代的 NBE 在加速限制周转的氧化加成步骤中的独特作用。