(1RS,4RS,5RS)-4-bromo-6-oxabicyclo<3.2.1>octan-7-one | 19914-91-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1RS,4RS,5RS)-4-bromo-6-oxabicyclo<3.2.1>octan-7-one
• 英文别名: 4-bromo-6-oxabicyclo<3.2.1>octan-7-one；4-bromo-6-oxabicyclo[3.2.1]octan-7-one；(+/-)-4exo-bromo-6-oxa-bicyclo[3.2.1]octan-7-one；(+/-)-4exo-Brom-6-oxa-bicyclo[3.2.1]octan-7-on；(1R,4R,5R)-4-bromo-6-oxabicyclo[3.2.1]octan-7-one
• CAS: 19914-91-1
• 化学式: C₇H₉BrO₂
• 分子量: 205.051
• InChiKey: HIEDNXSBEYNHJB-HSUXUTPPSA-N

物化性质

• 沸点：
  324.2±25.0 °C(Predicted)
• 密度：
  1.642±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  (1RS,4RS,5RS)-4-bromo-6-oxabicyclo<3.2.1>octan-7-one 在 盐酸 、 sodium hydroxide 、 dimethyl sulfide borane 、 lithium perchlorate 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 异丙醇 为溶剂， 反应 69.0h， 生成 c-4-<(benzyloxy)methyl>-t-2-methoxyy-r-1-cyclohexanol
  参考文献：
  名称：

  Regiochemical control of the ring-opening of 1,2-epoxides by means of chelating processes. 2. Synthesis and reactions of the cis- and trans-oxides of 4-[(benzyloxy)methyl]cyclohexene, 3-cyclohexenemethanol, and methyl 3-cyclohexenecarboxylate

  摘要：

  The synthesis of the diastereoisomeric epoxides cis-1b-d and trans-2b-d and the products of their ring-opening by various nucleophiles are described. The results of the ring-openings of the trans-epoxides 2b-d can be rationalized by combining stereoelectronic and conformational arguments. However, the regioselectivity of the ring-openings of the cis-epoxides 1b-d can, in principle, be influenced by the chelation of a metal ion by the oxygen atom of the epoxy group and that of the substituent on the 4-position. The results of the reactions of the cis-epoxides 1b-d indicate that, to some degree, chelation is indeed a factor. How important a factor it is is dependent both on the reaction conditions and on the concentration and nature of the metal ion. In the ring-openings of the cis-epoxides 1b and 1d, chelation seems to be a larger factor than it is in the ring-openings of cis-epoxide 1c. However, in no case is chelation as large a factor as it was in the ring-openings of the cis-epoxide 1a, which was studied earlier. On the other hand, the autocatalyzed methanolysis, under neutral conditions, of epoxy acid 1e, followed by CH2N2 methylation of the crude product, afforded a mixture of the two regioisomeric hydroxy ethers in which the C-2-type compound predominates. This result suggests that intramolecular hydrogen bonding may determine the reactive conformation of 1e.

  DOI：

  10.1021/jo00031a018
• 作为产物：
  描述：

  3-环己烯-1-甲酸 在 5,6-difluoro-2-(1-phenylethyl)benzo[d][1,2]selenazol-3(2H)-one 、 溴 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 7.0h， 以86%的产率得到(1RS,4RS,5RS)-4-bromo-6-oxabicyclo<3.2.1>octan-7-one
  参考文献：
  名称：

  异硒唑啉酮作为活化溴的催化剂：烯酸的溴内酯化和醇的氧化

  摘要：

  异硒烯酮是通过2-卤代苯甲酰胺与硒粉之间的铜催化Se-N键形成反应合成的。研究了异戊烯酮在戊-4-烯酸的溴化中的催化活性。研究了异壬烯酮9在以下反应中的催化剂：在碳酸钾为碱的情况下，用溴或N-溴丁二酰亚胺（NBS）溴化一系列链烯酸，使用NBS以及一系列其他方法对一系列烯烃进行溴酯化羧酸，以及使用溴作为氧化剂将仲醇氧化为酮。77揭示了异硒唑啉酮催化的溴化反应的机理细节Se NMR光谱和ES-MS研究。将溴氧化添加至异硒唑啉酮可得到二溴异硒唑酮（IV），这可能是反应条件下溴的活化的原因。从空间位阻效应Ñ苯基乙基对isoselenazolone和的酰胺基团的吸电子的isoselenazolone的苯并稠合的环上的取代基氟出现增强isoselenazolone的稳定性作为用于溴化反应的催化剂。

  DOI：

  10.1021/jo301486c

文献信息

• Asymmetric Synthesis of Optically Active 3-Cyclohexene-1-carboxylic Acid Utilizing Lactic Ester as a Chiral Auxiliary in the Diastereoselective Diels–Alder Reaction
  作者：Hidenori Ochiai、Wakana Hayashi、Akira Nishiyama、Ryunosuke Fujita、Shunichi Kubota、Miwa Sasagawa、Tatsuya Nishi

  DOI：10.1021/acs.oprd.1c00430

  日期：2022.3.18

  The optically active 3-cyclohexene-1-carboxylic acid was synthesized through a TiCl4-catalyzed diastereoselective Diels–Alder reaction utilizing lactic acid ester as a chiral auxiliary, which can be removed by washing with H2O. The (S)- and (R)-isomers were both derived from easily available ethyl l-lactate.

  使用乳酸酯作为手性助剂，通过 TiCl 4催化的非对映选择性 Diels-Alder 反应合成光学活性的 3-环己烯-1-羧酸，可以通过 H 2 O洗涤去除。 ( R )-异构体均衍生自容易获得的L-乳酸乙酯。
• Development of an Efficient Manufacturing Process for a Key Intermediate in the Synthesis of Edoxaban
  作者：Makoto Michida、Hideaki Ishikawa、Takeshi Kaneda、Shinya Tatekabe、Yoshitaka Nakamura

  DOI：10.1021/acs.oprd.8b00413

  日期：2019.4.19

  We report the development of a novel synthetic method to access a key intermediate in the synthesis of edoxaban. The main features of the new synthetic method are an improvement in the approach for the synthesis of a key chiral bromolactone, application of an interesting cyclization reaction utilizing neighboring group participation to construct a differentially protected 1,2-cis-diamine, and implementation

  我们报告了一种新型合成方法的开发，该方法可用于合成edoxaban的关键中间体。新的合成方法的主要特征是对关键手性溴内酯的合成方法进行了改进，利用邻近基团的参与进行有趣的环化反应以构建差异保护的1,2-顺式-二胺以及应用了塞子技术-流反应器技术可使不稳定的中间体反应成几百公斤规模。通过实施这些更改，可明显提高制备依多沙班的总产量，并导致更高效，更环保的生产过程。
• 一种顺式-3-羟基-环戊烷羧酸酯或环己烷羧 酸酯及其衍生物的合成方法
  申请人：南京药石科技股份有限公司

  公开号：CN107778168B

  公开（公告）日：2020-10-27

  本发明公开了一种顺式‑3‑羟基‑环戊烷羧酸酯或环已烷羧酸酯及其衍生物的合成方法，该方法以化合物III为原料，在碱和催化剂存在的条件下，与氢气在溶剂中仅通过一步开环反应就可以制备出顺式‑3‑羟基‑环戊烷羧酸酯或环已烷羧酸酯及其衍生物。该方法简便可行，并且获得的产物收率高、适用于规模生产。
• Novel Bromolactonization Using a Dimethyl Sulfoxide-Trimethylsilyl Bromide-Amine System; Unusual cis-Addition of trans-6-Substituted 3-Cyclohexene-1-carboxylic Acids
  作者：Chuzo Iwata、Akira Tanaka、Hiroaki Minuzo、Kazuyki Miyashita

  DOI：10.3987/com-90-5374

  日期：——
• Molecular sieves as an efficient and recyclable catalyst for bromolactonization and bromoacetoxylation reactions
  作者：Feng Chen、Xiaojian Jiang、Jun Cheng Er、Ying-Yeung Yeung

  DOI：10.1016/j.tetlet.2010.04.113

  日期：2010.6

  Bromolactonization of unsaturated acids and bromoacetoxylation of olefins proceeded smoothly in the presence of molecular sieves and N-bromosuccinimide. The molecular sieves can be recycled and reused, and the halogen carrier can be recovered effectively. (C) 2010 Elsevier Ltd. All rights reserved.