2-(2-Bromobenzyl)-1,3-cyclohexanedione | 134079-02-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(2-Bromobenzyl)-1,3-cyclohexanedione
• 英文别名: 2-(2-bromobenzyl)-1,3-cyclohexandione；2-(2-bromobenzyl)-cyclohexane-1,3-dione；2-[(2-Bromophenyl)methyl]cyclohexane-1,3-dione
• CAS: 134079-02-0
• 化学式: C₁₃H₁₃BrO₂
• 分子量: 281.149
• InChiKey: DCZPPRYIGSGPIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2-Bromobenzyl)-1,3-cyclohexanedione 在 N-甲基吡咯烷酮 、 四(三苯基膦)钯 、 <3THF*Mg2Cl2O*TiNCO> 作用下， 反应 12.0h， 以75%的产率得到1-oxo-1,2,3,4-tetrahydro-arcidine
  参考文献：
  名称：

  New C–N–C bond formation reaction using the nitrogenation-transmetallation process

  摘要：

  酮与芳基或乙烯基卤化物在钛异氰酸酯络合物[3THF·Mg2Cl2O·TiNCO]1和钯催化剂的存在下发生偶联反应，生成二乙烯基或芳基乙烯基胺，过程通过钛亚胺络合物6与芳基或乙烯基钯溴化物的金属间转移实现（THF为四氢呋喃）。

  DOI：

  10.1039/c39910000081
• 作为产物：
  描述：

  1,3-环己二酮 、 2-溴溴苄 在 氢氧化钾 作用下， 以 水 为溶剂， 反应 120.0h， 以64%的产率得到2-(2-Bromobenzyl)-1,3-cyclohexanedione
  参考文献：
  名称：

  一锅法反应：对映体纯的双环[5.3.1]十一烷；紫杉类化合物的合成

  摘要：

  C-2取代的环己烯酮与对映体纯的α-溴戊烯酸酯反应，生成对映体纯的三环辛烷，可以将其转变为具有典型双环[5.3.1]十一烷骨架的紫杉烷样化合物。

  DOI：

  10.1016/j.tet.2004.06.094

文献信息

• A new method for the synthesis of difluoromethyl enol ethers by O-difluoromethylation of 1,3-diones with ClCF₂CO₂Et
  作者：Xiaoxi Lin、Zhiqiang Weng

  DOI：10.1039/c5ob00020c

  日期：——

  single-step protocol for the synthesis of difluoromethyl enol ether derivatives by O-difluoromethylation of 1,3-diones via in situ generation of difluorocarbene from ClCF2CO2Et has been developed. The functional group tolerance, scalability of the reaction, and mild reaction conditions make it an attractive protocol for the synthesis of biologically relevant difluoromethyl ethers of interest to the pharmaceutical

  已经开发了一种简便，有效的单步骤方案，该方案通过从ClCF2CO2Et原位生成二氟卡宾，通过1,3-二酮的O-二氟甲基化合成二氟甲基烯醇醚衍生物。官能团耐受性，反应的可扩展性和温和的反应条件使其成为合成制药和农用化学工业感兴趣的生物学相关二氟甲基醚的有吸引力的方案。
• Chiral Brønsted Acid-Promoted Enantioselective Desymmetrization in an Intramolecular Schmidt Reaction of Symmetric Azido 1,3-Hexanediones: Asymmetric Synthesis of Azaquaternary Pyrroloazepine Skeletons
  作者：Ming Yang、Yu-Ming Zhao、Shu-Yu Zhang、Yong-Qiang Tu、Fu-Min Zhang

  DOI：10.1002/asia.201100171

  日期：2011.6.6

  The enantioselective desymmetrization of 2‐substituted‐2‐azidopropyl 1,3‐hexanediones through an asymmetric intramolecular Schmidt reaction using a chiral Brønsted acid has been developed for the first time. Synthetically interesting pyrroloazepine skeletons with an azaquaternary stereogenic center with up to 59 % ee are accessed effectively (see scheme; R=H, alkyl, or aryl).

  首次开发了使用手性布朗斯台德酸通过不对称分子内Schmidt反应对2-取代2-叠氮丙基1,3-己二酮进行对映选择性脱对称。合成有趣的吡咯并ze庚因骨架，其氮杂季铵立体异构中心的ee高达59％（请参阅方案； R = H，烷基或芳基）。
• Organocatalytic enantioselective desymmetrization of enal-tethered cyclohexane-1,3-diones
  作者：Lakshmi Revati Magham、Abdus Samad、Satish B. Thopate、Jagadeesh Babu Nanubolu、Rambabu Chegondi

  DOI：10.1039/d4cc00487f

  日期：——

  Organocatalytic asymmetric desymmetrization of prochiral cyclohexane-1,3-diones has been demonstrated through the merging of iminium and enamine activation. The tandem annulation reaction proceeds through a sequential oxa-Michael addition/intramolecular aldol reaction/[1,3]-amino oxetane rearrangement pathway. Mechanistic study using an 18O-water experiment suggests oxetane rearrangement instead of

  前手性环己烷-1,3-二酮的有机催化不对称去对称作用已通过亚胺和烯胺活化的合并得到证实。串联成环反应通过连续的 oxa-Michael 加成/分子内羟醛反应/[1,3]-氨基氧杂环丁烷重排途径进行。使用18 O-水实验进行的机理研究表明氧杂环丁烷重排而不是直接脱水。没有观察到通过烷氧基消除形成其他竞争性 Rauhut-Currier 产物。
• O-Arylation versus C-Arylation:  Copper-Catalyzed Intramolecular Coupling of Aryl Bromides with 1,3-Dicarbonyls
  作者：Yewen Fang、Chaozhong Li

  DOI：10.1021/jo060747t

  日期：2006.8.1

  The copper-catalyzed intramolecular coupling of aryl bromides with 1,3-dicarbonyls via a six-membered ring closure was examined. With CuI (10 mol %) as the catalyst, N,N'-dimethylethylenediamine as the ligand, and Cs2CO3 as the base, the reactions of alpha-(2-bromobenzyl)-beta-keto esters in THF at refluxing temperature afforded the corresponding substituted 4H-1-benzopyrans in high yields via O-arylation. On the other hand, the reactions of delta-(2-bromophenyl)-beta-keto esters in refluxing dioxane led to the formation of 3,4-dihydronaphthalen-2(1H)-one derivatives via C-arylation.
• Selective O-difluoromethylation of 1,3-diones using S-(difluoromethyl) sulfonium salt
  作者：Guo-Kai Liu、Xin Li、Wen-Bing Qin、Wei-Feng Lin、Li-Ting Lin、Jia-Yi Chen、Jian-Jian Liu

  DOI：10.1016/j.cclet.2019.03.036

  日期：2019.8

  A facile and highly efficient approach for selective O-difluoromethylation of 1,3-diones by recently developed bench-stable S-(difluoromethyl)sulfonium salt was described. And a broad range of difluoromthyl enol ethers were readily accessed in good to excellent yields under mild reaction conditions. Mechanistic studies revealed that the O-difluoromethylation reaction proceeds mainly via a difluorocarbene pathway. (C) 2019 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.