(R)-cyclohex-2-en-1-yl 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: (R)-cyclohex-2-en-1-yl benzoate
• 英文别名: (R)-2-cyclohexenyl benzoate；(R)-2-cyclohexenyl-1-benzoate；[(1R)-cyclohex-2-en-1-yl] benzoate
• 化学式: C₁₃H₁₄O₂
• 分子量: 202.253
• InChiKey: APZIYLKXAJJSIZ-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-(tosyloxy)cyclohexyl benzoate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 以80%的产率得到(R)-cyclohex-2-en-1-yl benzoate
  参考文献：
  名称：

  Copper complex catalyzed asymmetric monosulfonylation of meso-vic-diols

  摘要：

  A symmetric desymmetrization of meso-vic-diols was performed by tosylation in the presence of copper(II) triflate and (R,R)-Ph-BOX as a catalyst. The method was successfully applied to asymmetric desymmetrization of cyclic and acyclic meso-vic-diols in high enantioselectivity with up to >99% ee. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.08.104

文献信息

• Studies on enantioselective allylic oxidation of olefins using peresters catalyzed by Cu(i)-complexes of chiral pybox ligands
  作者：Sandeep K. Ginotra、Vinod K. Singh

  DOI：10.1039/b612423b

  日期：——

  Enantioselective allylic oxidation of olefins with various peresters, using a catalytic amount of Cu(I)-pybox complex, can be tuned to achieve high asymmetric induction (up to 98% ee) by choosing a unique combination of a ligand and a perester at room temperature. The asymmetric induction in the reaction strongly depends on the nature of the substituents attached to the aryl ring of peresters. The

  通过在室温下选择配体和perester的独特组合，可以调节催化量的Cu（I）-pybox配合物与各种过酸酯的烯烃的对映选择性烯丙基氧化，以实现高不对称诱导（最高98％ee）。温度。反应中的不对称诱导在很大程度上取决于与过酸酯的芳环相连的取代基的性质。对于高对映选择性而言，在C-5处存在宝石二苯基和在恶唑啉环的手性中心（C-4）处存在仲或叔烷基取代基是至关重要的。已提出并讨论了pi-pi堆积模型以解释反应的立体化学结果。
• Copper(II) complexes of pyridine-oxazoline (Pyox) ligands: Coordination chemistry, ligand stability, and catalysis
  作者：Andrew J. Hallett、Thomas M. O’Brien、Emma Carter、Benson M. Kariuki、Damien M. Murphy、Benjamin D. Ward

  DOI：10.1016/j.ica.2015.10.032

  日期：2016.2

  The coordination chemistry of copper(II) complexes bearing pyridine-oxazoline (“Pyox”) ligands has been studied, with an aim of investigating their catalytic ability. Interestingly, the stability of the coordinated ligands has been shown to be much less than previously assumed: hydrolysis of the ligands by fortuitous water gives rise to 2-pyridine carboxylate formation, which encapsulate the copper

  已经研究了带有吡啶-恶唑啉（“ Pyox”）配体的铜（II）配合物的配位化学，旨在研究其催化能力。有趣的是，已证明配位配体的稳定性远低于先前的假设：偶然的水使配体水解会生成2-吡啶羧酸盐，从而将铜包封在二维配位聚合物3中。 [Cu（R-Pyox）（NCMe）2（ClO4）2] R =苄基（Bn）2a，苯基（Ph）2b，异丙基（iPr）2c}的制备，其中的苄基衍生物已通过CW EPR光谱。配合物[Cu（Bn-Pyox）（NCMe）2（ClO 4）2]和上述配位聚合物已经在晶体学上进行了表征。
• Catalytic enantioselective rearrangement of meso-epoxides mediated by chiral lithium amides in the presence of excess cross-linked polymer-bound lithium amides
  作者：Atsushi Seki、Masatoshi Asami

  DOI：10.1016/s0040-4020(02)00371-x

  日期：2002.6

  Insoluble polymer-bound achiral lithium dialkylamides were prepared from the corresponding cross-linked polymer-bound amines and butyllithium. The polymer-bound achiral reagent was applied to a catalytic enantioselective rearrangement of meso-epoxides as an in situ regenerating agent of a chiral lithium amide. The efficiency of the catalytic system was improved, and chiral allylic alcohol derivatives

  由相应的交联的与聚合物结合的胺和丁基锂制备了不溶的与聚合物结合的非手性锂二烷基酰胺。将与聚合物结合的非手性试剂应用于作为手性锂酰胺的原位再生剂的内消旋环氧化物的催化对映选择性重排。改进了催化系统的效率，并通过使用过量的聚合物结合试剂和亚化学计量的手性锂酰胺，以（2 S，3a S，7a S）制备了高对映体过量的手性烯丙醇衍生物。-2-（吡咯烷基-1-基甲基）八氢吲哚。该反应成功地用于合成（1 S，4 R）-4-苯甲酰氨基-2-环戊烯醇，一种有用的手性合成中间体，用于碳环核苷，含量为97％ee。
• Enantioselective allylic oxidation catalyzed by chiral bisoxazoline-copper complexes
  作者：Abha S. Gokhale、Alexander B.E. Minidis、Andreas Pfaltz

  DOI：10.1016/0040-4039(95)00140-8

  日期：1995.3

  Copper(I) complexes prepared in situ from chiral bisoxazolines and Cu(I)OTf have been studied as catalysts for the allylic oxidation of cycloalkenes. Using 5 mol% of catalyst and tertbutyl perbenzoate as oxidant, optically active 2-cycloalkenyl benzoates were obtained in moderate to good yields. The highest enantiomeric excesses, 74% at 23 °C and up to 84% at lower temperatures, were observed for cyclopentene

  已经研究了由手性双恶唑啉和Cu（I）OTf原位制备的铜（I）配合物作为环烯烃烯丙基氧化的催化剂。使用5mol％的催化剂和过苯甲酸叔丁酯作为氧化剂，以中等至良好的产率获得了光学活性的2-环烯基苯甲酸酯。对环戊烯和环庚烯的对映体过量最高，在23°C时高达74％，在较低温度下高达84％，而环己烯的选择性较低，介于64–77％ee之间。
• Designing chiral amido-oxazolines as new chelating ligands devoted to direct Cu-catalyzed oxidation of allylic C H bonds in cyclic olefins
  作者：Saadi Samadi、Khosrow Jadidi、Mojgan Samadi、Akram Ashouri、Behrouz Notash

  DOI：10.1016/j.tet.2018.12.062

  日期：2019.2

  characterization of the complex confirmed the involvement of both dentate parts of the ligands, the oxygen and nitrogen atoms, in complexation with copper. The utilization of this amido-oxazoline ligands in the copper-catalyzed enantioselective esterification of allylic CH bonds of cyclic olefins with tert-butyl-4-nitrobenzoperoxoate resulted in the highest activities, yields (up to 95%) and enantioselectivities

  从廉价和可商购的材料中方便地合成了新型的酰胺基-恶唑啉配体，其产率高且对映体过量。与此类配体的相应的手性铜络合物[C 2对称的小号，小号双（酰氨基-恶唑啉铜（II）复合物]进行了相应的合成。配体的ORTEP图6A和复杂6A进行了比较和表征-铜该配合物证实了配体的两个齿状部分（氧和氮原子）均与铜络合，该酰胺基-恶唑啉配体在铜催化的环烯烃的烯丙基C H键的对映选择性酯化中的利用在HZSM-5沸石的存在下，4-硝基苯并过氧叔丁基叔丁基酯具有最高的活性，最高收率（高达95％）和对映选择性（最高96％）。与文献中报道的其他方法相比，这些新发现突显了该协议是氧化环烯烃不对称烯丙基CH键的最有吸引力和最有用的方法之一。