(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

• Isoselenazolones as Catalysts for the Activation of Bromine: Bromolactonization of Alkenoic Acids and Oxidation of Alcohols
  作者：Shah Jaimin Balkrishna、Ch Durga Prasad、Piyush Panini、Michael R. Detty、Deepak Chopra、Sangit Kumar

  DOI：10.1021/jo301486c

  日期：2012.11.2

  selenium powder. The catalytic activity of the various isoselenazolones was studied in the bromolactonization of pent-4-enoic acid. Isoselenazolone 9 was studied as a catalyst in several reactions: the bromolactonization of a series of alkenoic acids with bromine or N-bromosuccinimide (NBS) in the presence of potassium carbonate as base, the bromoesterification of a series of alkenes using NBS and a variety

  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。
• 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。
• 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.