2-bromo-1-cyclooctene-1-carbaldehyde | 64825-11-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 2-bromo-1-cyclooctene-1-carbaldehyde
• 英文别名: (Z)-2-bromocyclooct-1-ene-1-carbaldehyde；(Z)-2-bromocyclooct-1-enecarbaldehyde；2-Brom-cyclooct-1-enal；(Z)-2-bromocyclo-1-octenecarbaldehyde；(1Z)-2-bromocyclooctene-1-carbaldehyde
• CAS: 64825-11-2
• 化学式: C₉H₁₃BrO
• 分子量: 217.106
• InChiKey: TYUYHTIQICUCJI-HJWRWDBZSA-N

物化性质

• 沸点：
  70-72 °C(Press: 0.9 Torr)
• 密度：
  1.426±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  2-bromo-1-cyclooctene-1-carbaldehyde 在 四(三苯基膦)钯 、 镍 氢气 、 铜 作用下， 以 乙醇 、 二甲基亚砜 为溶剂， 反应 6.5h， 生成 8-Azatricyclo[8.6.0.02,7]hexadeca-1(10),2,4,6,8-pentaene
  参考文献：
  名称：

  New protocols for the synthesis of 3,4-annulated and 4-substituted quinolines from β-bromo-α,β-unsaturated aldehydes and 1-bromo-2-nitrobenzene or 2-bromoacetanilide

  摘要：

  The palladium[0]-mediated Ullmann cross-coupling of readily available beta-bromo-alpha,beta-unsaturated aldehydes of the general form 2 with 1-bromo-2-nitrobenzene (3, X = Br) delivers products, 4, that undergo reductive cyclization to novel quinolines (5) upon exposure to indium in aqueous ammonium chloride or to Raney-nickel in the presence of dihydrogen. Analogous cross-coupling of 2-bromoacetanilide (6) with 2 affords products of type 7 that undergo in situ and K2CO3-mediated cyclization to give the same types of quinolines (5). (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.03.078
• 作为产物：
  描述：

  环辛酮 、 N,N-二甲基甲酰胺 在 三溴化磷 作用下， 以 二氯甲烷 为溶剂， 反应 0.66h， 生成 2-bromo-1-cyclooctene-1-carbaldehyde
  参考文献：
  名称：

  Discovery of an Orally Bioavailable Small Molecule Inhibitor of Prosurvival B-Cell Lymphoma 2 Proteins

  摘要：

  Overexpression of prosurvival proteins such as Bcl-2 and Bcl-X-L has been correlated with tumorigenesis and resistance to chemotherapy, and thus, the development of antagonists of these proteins may provide a novel means for the treatment of cancer. We recently described the discovery of 1 (ABT-737), which binds Bcl-2, Bcl-X-L, and Bcl-w with high affinity, shows robust antitumor activity in murine tumor xenograft models, but is not orally bioavailable. Herein, we report that targeted modifications at three key positions of 1 resulted in a 20-fold improvement in the pharmacokinetic/pharmacodynamic relationship (PK/PD) between oral exposure (AUC) and in vitro efficacy in human tumor cell lines (EC50). The resulting compound, 2 (ABT-263), is orally efficacious in an established xenograft model of human small cell lung cancer, inducing complete tumor regressions in all animals. Compound 2 is currently in multiple phase 1 clinical trials in patients with small cell lung cancer and hematological malignancies.

  DOI：

  10.1021/jm800669s

文献信息

• The Dipolar Route to Azepin-3-one Derivatives by Heterocyclization of Linear and Monocyclic Enallenyl Nitrones as the Key Step
  作者：Karin Knobloch、Joachim Koch、Manfred Keller、Wolfgang Eberbach

  DOI：10.1002/ejoc.200400922

  日期：2005.7

  synthesis of structurally different systems including the monocyclic derivatives 17 and 18, the bicyclic azepinones 10a–d, and the tricyclic heterocycles 37–40, 42, 43, 45, 47, and 48. In addition, the applicability of the reaction principle was demonstrated through the preparation of the benzo-piperidino compound 52 which acts as a model compound for the alkaloid astrocasine (53). A multistep reaction mechanism

  最近发现的苯并戊烯基硝酮转化为 1,2-二氢苯并 [c] azepin-3-ones 已扩展到结构不同的系统的合成，包括单环衍生物 17 和 18、双环 azepinones 10a-d 和三环杂环37-40、42、43、45、47 和 48。此外，通过制备作为生物碱 astrocasine 模型化合物的苯并哌啶基化合物 52 证明了反应原理的适用性 (53)。提出了一种多步反应机制，涉及烯基硝酮作为 1,7-偶极电环化过程的前体，然后进行进一步的键重组。在某些情况下，异吲哚（41、44 和 46）作为次要产物的形成支持环丙酮（E 型和 H 型）作为中间体的出现。对选定的二氢氮杂环酮进行光化学研究得出了不同的结果：虽然单环氮杂环庚酮 17 在直接和敏化激发下反应形成双环非对映异构体 20 和 21，但双环化合物 10 的反应更为复杂。仅观察到 10a、b 在直接照射下发生 4π-环化反应，导致在
• Synthesis of Carbocyclic Aromatic Compounds Using Ruthenium-Catalyzed Ring-Closing Enyne Metathesis
  作者：Hidetoshi Takahashi、Kazuhiro Yoshida、Akira Yanagisawa

  DOI：10.1021/jo900456g

  日期：2009.5.15

  3-halo-2-propene-1-ols 13 by utilizing combinations of the Sonogashira coupling, allylation, and the Dess−Martin oxidation. The RCEM/dehydration for the synthesis of 1,3,5-tris(1-phenylethenyl)benzene derivative 4r and the RCEM/RCM/dehydration for the synthesis of 1,1′-binaphthyl derivative 19a are also presented as applications of this method.

  报道了取代的碳环芳族化合物的一般合成方法。1,5-辛二烯-7-yn-4-ols 6的闭环烯炔复分解（RCEM）/脱水和1,5-辛二烯-7-yn-4-ones 7的RCEM /互变异构提供了多种取代基分别为苯乙烯4和4-乙烯基苯酚8。通过使用Sonogashira偶联，烯丙基化和Dess-Martin氧化的组合，可以轻松地从β-卤代-α，β-不饱和醛9或3-卤代-2-丙烯-1-醇13制备无环前体6和7。RCEM /脱水法合成1,3,5-三（1-苯基乙烯基）苯衍生物4r作为该方法的应用，还提出了用于合成1,1'-联萘衍生物19a的RCEM / RCM /脱水方法。
• Lewis Acid Catalyzed Intramolecular [3 + 2] Cross Cycloadditions of Cobalt-Alkynylcyclopropane 1,1-Diesters with Carbonyls for Construction of Medium-Sized and Polycyclic Skeletons
  作者：Junhui Zhang、Siyang Xing、Jun Ren、Shende Jiang、Zhongwen Wang

  DOI：10.1021/ol503285u

  日期：2015.1.16

  A Lewis acid catalyzed intramolecular [3 + 2] cross cycloaddition of cobalt-alkynylcyclopropane 1,1-diesters with carbonyls has been successfully developed. Together with simple and efficient postcycloadditions of the cobalt-alkyne moiety, a general and efficient strategy for construction of structurally complex and diverse medium-sized skeletons and related polycycles was supplied successfully.

  已经成功开发了路易斯酸催化的钴-炔基环丙烷1,1-二酯与羰基的分子内[3 + 2]交叉环加成反应。连同钴炔基部分的简单有效的环加成反应，成功地提供了构建结构复杂多样的中型骨架和相​​关多环的通用有效策略。
• Synthesis of alkyl 2,5-dihydro-5-oxofuran-2-carboxylates via palladium-catalyzed carbonylative cyclization of β-bromovinyl aldehydes in alcohols
  作者：Chan Sik Cho、Jun Uk Kim、Heung-Jin Choi

  DOI：10.1016/j.jorganchem.2008.09.014

  日期：2008.11

  β-Bromovinyl aldehydes reacts with carbon monoxide and alcohols at 125 °C in the presence of a catalytic amount of a palladium catalyst along with a base to give the corresponding carbonylative cyclized alkyl 2,5-dihydro-5-oxofuran-2-carboxylates in good yields. A reaction pathway involving intramolecular addition of acylpalladium to formyl group is proposed as a key step of this catalytic process.

  在催化量的钯催化剂和碱的存在下，β-溴乙烯基醛在125°C下与一氧化碳和醇反应，生成相应的羰基环化烷基2,5-二氢-5-氧呋喃-2-羧酸酯良品率高。提出了将酰基铝分子内加成到甲酰基的反应途径，作为该催化过程的关键步骤。
• Mild Approach to 2-Acylfurans via Intercepted Meyer–Schuster Rearrangement of 6-Hydroxyhex-2-en-4-ynals
  作者：Prabhakararao Tharra、Beeraiah Baire

  DOI：10.1021/acs.joc.5b01420

  日期：2015.8.21

  Meyer–Schuster (M-S) rearrangement for the synthesis of 2-acylfurans from corresponding cis-6-hydroxyhex-2-en-4-ynals. This reaction was found to be very general, and the starting materials are easily accessible. By this methodology the first synthesis of deoxy-nor-abiesesquine B, a sesquiterpene, was also achieved in three steps. The concept of adding two nucleophiles during the M-S rearrangement was introduced

  我们已经开发出一种温和的，分子内截获的Meyer-Schuster（MS）重排技术，用于从相应的顺式-6-羟基己二-2-烯-4-醛合成2-酰基呋喃。发现该反应非常普遍，并且起始原料容易获得。通过这种方法脱氧的第一合成也不-abiesesquine B，倍半萜烯，也被在三个步骤中实现。介绍了在MS重排过程中添加两个亲核试剂的概念。