2-bromocyclohexyl benzoate

• 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-bromocyclohexyl benzoate
• 英文别名: [(1S,2S)-2-bromocyclohexyl] benzoate
• 化学式: C₁₃H₁₅BrO₂
• 分子量: 283.165
• InChiKey: OWOLJQMJMUJTGJ-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  2-bromocyclohexyl benzoate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 反应 3.0h， 以84%的产率得到2-环己烯-1-基苯甲酸酯
  参考文献：
  名称：

  Substrate modification to increase the enantioselectivity of hydrolases. A route to optically-active cyclic allylic alcohols.

  摘要：

  The esterase-catalyzed resolution of the cyclic allylic acetates - 1-acetyloxy-2-cyclopentene, 1-acetyloxy-2-cyclohexene, and 1-acetyloxy-2-cycloheptene - was not enantioselective. We hypothesized that this inefficiency stems from the similarity in size of the substituents at the stereocenter (CH2-CH2 vs. CH=CH). To increase the enantioselectivity, we resolved precursors to these cyclic allylic alcohols: esters of trans-2-bromocycloalkanols (C5, C6, C7). These esters had a larger difference in the size of the substituents (CH2 vs. CHBr) at the stereocenter and were efficiently resolved by both cholesterol esterase and lipase from Pseudomonas cepacia (Amano P, PCL). A synthetic-scale resolution with PCL yielded the (1S,2S)-1-butanoyloxy-2-bromocycloalkanes in >98% ee. Heating with DBU to eliminate HBr, followed by reduction with LiAlH4 to cleave the ester, yielded the allylic alcohols: (S)-(-)-2-cyclopenten-1-ol (65% ee), (S)-(-)-2-cyclohexen-1-ol (>99% ee), and (S)-(-)-2-cyclohepten-1-ol (>98% ee).

  DOI：

  10.1016/s0957-4166(00)80126-3
• 作为产物：
  描述：

  silver benzoate 在 四氯化碳 、 溴 作用下， 生成 2-bromocyclohexyl benzoate
  参考文献：
  名称：

  Uschakow; Tschistow; Schlossberg, Zhurnal Obshchei Khimii, 1935, vol. 5, p. 1397

  摘要：

  DOI：

文献信息

• Lanthanoid-catalyzed ring-opening reaction of epoxides with acyl halides
  作者：Yuki Taniguchi、Shintaro Tanaka、Tsugio Kitamura、Yuzo Fujiwara

  DOI：10.1016/s0040-4039(98)00831-4

  日期：1998.6

  Eu(dpm)3 [dpm: dipivaloylmethanate] catalyzes the ring-opening reaction of epoxides with acyl halides affording the corresponding 2-haloalkyl esters. The stereochemical course was confirmed as trans-addition in the case of the reaction of cyclohexene oxide.

  Eu（dpm）3 [dpm：二新戊酰基甲酸酯]催化环氧化物与酰基卤的开环反应，得到相应的2-卤代烷基酯。在环己烯氧化物反应的情况下，立体化学过程被确认为反式加成。
• Enantioselective Synthesis of Vicinal Halohydrins via Dynamic Kinetic Resolution
  作者：Abel Ros、Antonio Magriz、Hansjörg Dietrich、Rosario Fernández、Eleuterio Alvarez、José M. Lassaletta

  DOI：10.1021/ol052821k

  日期：2006.1.1

  [reaction: see text] Expanding the scope of enantioselective catalysis via DKR, transfer hydrogenation of a variety of cyclic alpha-halo ketones was accomplished using the Noyori/Ikariya (R,R)- or (S,S)-I catalysts and either HCO(2)H/Et(3)N or HCO(2)Na/n-Bu(4)NBr in H(2)O/CH(2)Cl(2) as the hydrogen sources. Good yields of vicinal bromo-, chloro-, and fluorohydrins with excellent de and ee levels were

  [反应：见正文]使用Noyori / Ikariya（R，R）-或（S，S）-I催化剂，通过DKR扩大了对映选择性催化的范围，转移了各种环状α-卤代酮的氢化反应HCO（2）H / Et（3）N或H（2）O / CH（2）Cl（2）中的HCO（2）Na / n-Bu（4）NBr作为氢源。在大多数情况下，只需简单调整反应条件，即可获得具有优良de和ee水平的邻位溴代，氯代和氟代醇的良好收率。
• Trifluoromethylation of Alkyl Radicals in Aqueous Solution
  作者：Haigen Shen、Zhonglin Liu、Pei Zhang、Xinqiang Tan、Zhenzhen Zhang、Chaozhong Li

  DOI：10.1021/jacs.7b06044

  日期：2017.7.26

  The copper-mediated trifluoromethylation of alkyl radicals is described. The combination of Et3SiH and K2S2O8 initiates the radical reactions of alkyl bromides or iodides with BPyCu(CF3)3 (BPy = 2,2'-bipyridine) in aqueous acetone at room temperature to afford the corresponding trifluoromethylation products in good yield. The protocol is applicable to various primary and secondary alkyl halides and

  描述了铜介导的烷基三氟甲基化。Et3SiH 和 K2S2O8 的组合在室温下在丙酮水溶液中引发烷基溴化物或碘化物与 BPyCu(CF3)3（BPy = 2,2'-联吡啶）的自由基反应，以良好的收率提供相应的三氟甲基化产物。该协议适用于各种一级和二级烷基卤化物，并具有广泛的官能团兼容性。提出了一种涉及三氟甲基从 Cu(II)-CF3 中间体转移到烷基自由基的机制。
• Nitroxyl Catalysts for Six-Membered Ring Bromolactonization and Intermolecular Bromoesterification of Alkenes with Carboxylic Acids
  作者：Katsuhiko Moriyama、Masako Kuramochi、Seiji Tsuzuki、Kozo Fujii、Takeshi Morita

  DOI：10.1021/acs.orglett.0c03546

  日期：2021.1.15

  includes a six-membered ring bromolactonization of alkenyl carboxylic acids catalyzed by AZADO as the nitroxyl radical catalyst, and an intermolecular bromoesterification of alkenes with carboxylic acids using NMO as the N-oxide catalyst. We also accomplished a remote diastereoselective bromohydroxylation via an AZADO-catalyzed six-membered ring bromolactonization and a subsequent ring cleavage reaction

  我们开发了一种用溴试剂进行的硝基氧催化烯烃的溴代酯化反应，其中包括由AZADO作为硝基氧基自由基催化剂催化的六元环烯基羧酸的环溴内酯化反应，以及使用NMO作为N-氧化物对烯烃与羧酸的分子间溴化酯化反应。催化剂。我们还通过AZADO催化的六元环溴内酰胺化以及随后与烷基胺的环裂解反应完成了远程非对映选择性溴羟基化反应，以提供具有高非对映选择性的ε-溴-δ-羟基酰胺。
• Solvent and catalyst-free bromofunctionalization of olefins using a mechanochemical approach
  作者：Jonathan Wong、Ying-Yeung Yeung

  DOI：10.1039/d1ra01816g

  日期：——

  Bromofunctionalizations of olefins are an important class of chemical transformations. N-Bromoimide reagents are commonly used in these reactions but catalysts and chlorinated solvents are often employed to achieve a reasonable reaction rate. In this report, we present a solvent and catalyst-free bromofunctionalization of olefins using mechanical force.

  烯烃的溴官能化是一类重要的化学转化。N-溴酰亚胺试剂通常用于这些反应，但通常使用催化剂和氯化溶剂来实现合理的反应速率。在本报告中，我们提出了一种使用机械力对烯烃进行无溶剂和无催化剂溴官能化的方法。