2-Cyclohexenyl p-(methoxycarbonyl)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-Cyclohexenyl p-(methoxycarbonyl)benzoate
• 英文别名: cyclohex-2-en-1-yl methyl tetrephthalate；cyclohex-2-en-1-yl methyl terephthalate；cyclohex-2-enyl methyl terephthalate；4-O-cyclohex-2-en-1-yl 1-O-methyl benzene-1,4-dicarboxylate
• 化学式: C₁₅H₁₆O₄
• 分子量: 260.29
• InChiKey: NDACAUSSPVQQGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-碘-丁酸乙酯 、 一氧化碳 、 2-Cyclohexenyl p-(methoxycarbonyl)benzoate 在 四(三苯基膦)钯 六甲基磷酰三胺 、 锌铜偶 作用下， 生成 Ethyl 5-(2-cyclohexenyl)-5-oxopentanoate
  参考文献：
  名称：

  Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide

  摘要：

  A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields under 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA. The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of unsymmetrical allylic substrates. For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts. The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and gamma-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers. In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions. Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.

  DOI：

  10.1021/jo00110a047
• 作为产物：
  描述：

  对苯二甲酸单甲酯 、 环己烯 在 二叔丁基过氧化物 、 C₁₁H₂₃N₂⁽¹⁺⁾*Br₄Fe^(1-) 作用下， 以 乙酸乙酯 为溶剂， 反应 24.0h， 以57%的产率得到2-Cyclohexenyl p-(methoxycarbonyl)benzoate
  参考文献：
  名称：

  铁催化的烯丙基sp 3 C–H键与羧酸的酯化反应：容易获得烯丙基酯

  摘要：

  的烯丙基属的第一一般高效的铁催化酯化3使用离子铁（III）络合物（羧酸C-H键的1 - 4作为催化剂和DTBP（DTBP =二）叔丁基过氧化物）作为氧化剂已完成。使用离子铁（III）配合物2作为催化剂，以5摩尔％的负载量，可以很好地合成各种烯丙基酯。该反应的特征在于其高效，广泛的底物范围，优异的位阻耐受性和良好的官能团相容性。

  DOI：

  10.1016/j.tetlet.2017.05.039

文献信息

• Copper-catalyzed oxidative coupling of acids with alkanes involving dehydrogenation: facile access to allylic esters and alkylalkenes
  作者：Cheng-Yong Wang、Ren-Jie Song、Wen-Ting Wei、Jian-Hong Fan、Jin-Heng Li

  DOI：10.1039/c4cc09393c

  日期：——

  We here describe a new copper-catalyzed oxidative coupling of acids with alkanes for the selective synthesis of allylic esters and alkylalkenes. This method achieves multiple dehydrogenation and esterification, representing a new unactivated C(sp(3))-H oxidative esterification of acids with common alkanes.

  我们在这里描述了一种新的铜催化的酸与烷烃的氧化偶联反应，用于选择性合成烯丙基酯和烷基烯烃。此方法实现多次脱氢和酯化反应，代表酸与普通烷烃的新的未活化的C（sp（3））-H氧化酯化反应。
• Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes
  作者：Ba L. Tran、Matthias Driess、John F. Hartwig

  DOI：10.1021/ja510093x

  日期：2014.12.10

  with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical

  我们报道了铜催化未活化烷烃与各种取代苯甲酸的氧化脱氢羧化（ODC），产生相应的烯丙酯。光谱研究（EPR、UV-vis）表明，催化剂的静止状态为 [(BPI)Cu(O2CPh)] (1-O2CPh)，由 [(BPI)Cu(PPh3)2]、氧化剂和苯甲酸形成酸。 1-O2CPh 与烷基和自由基探针的催化和化学计量反应表明，叔丁氧基自由基发生了 C-H 键断裂。此外，环己烷和d12-环己烷在不同容器中反应的氘动力学同位素效应表明，环己烷ODC的周转限制步骤是C-H键断裂。为了了解铜催化酰胺化和铜催化 ODC 形成的产物差异的根源，进行了烷基自由基与一系列羧酸铜、酰胺酸铜和亚氨酸铜络合物的反应。竞争实验结果表明，烷基自由基与铜配合物的相对反应速率遵循Cu(II)-amidate > Cu(II)-imidate > Cu(II)-苯甲酸盐的趋势。与这一趋势一致，在苯甲酰胺酯和苯甲酸酯上含有更多富电子芳基的
• NHPI- and TBAI-Co-Catalyzed Synthesis of Allylic Esters from Toluene Derivatives and Alkenes
  作者：Hongmei Deng、Xueshun Jia、Jian Li、Chengliang Li、Tao Jin、Chunju Li

  DOI：10.1055/s-0036-1591748

  日期：2018.4

  An N-hydroxyphthalimide (NHPI) and tetrabutylammonium iodide (TBAI) co-catalyzed oxidative coupling reaction of toluene derivatives and alkenes has been disclosed. This method can serve as a new strategy to access allylic ester using toluene derivatives as oxyacylating reagent. This metal-free protocol also features the readily available starting materials, broad substrate scope, and mild reaction

  已经公开了 N-羟基邻苯二甲酰亚胺 (NHPI) 和四丁基碘化铵 (TBAI) 共催化的甲苯衍生物和烯烃的氧化偶联反应。该方法可以作为使用甲苯衍生物作为氧酰化试剂获得烯丙酯的新策略。这种无金属协议还具有易于获得的起始材料、广泛的底物范围和温和的反应条件。
• Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide
  作者：Kengo Yasui、Keigo Fugami、Shuji Tanaka、Yoshinao Tamaru

  DOI：10.1021/jo00110a047

  日期：1995.3

  A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields under 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA. The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of unsymmetrical allylic substrates. For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts. The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and gamma-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers. In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions. Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.
• Iron-catalyzed esterification of allylic sp 3 C–H bonds with carboxylic acids: Facile access to allylic esters
  作者：Bing Lu、Fan Zhu、Dan Wang、Hongmei Sun、Qi Shen

  DOI：10.1016/j.tetlet.2017.05.039

  日期：2017.6

  iron-catalyzed esterification of allylic sp3 C–H bonds with carboxylic acids using ionic iron(III) complexes (1–4) as a catalyst and DTBP (DTBP = di-tert-butyl peroxide) as an oxidant is achieved. A variety of allylic esters were synthesized in good to excellent yields using the ionic iron(III) complex 2 as a catalyst in a 5 mol% loading. This reaction is characterized by its high efficiency, broad substrate

  的烯丙基属的第一一般高效的铁催化酯化3使用离子铁（III）络合物（羧酸C-H键的1 - 4作为催化剂和DTBP（DTBP =二）叔丁基过氧化物）作为氧化剂已完成。使用离子铁（III）配合物2作为催化剂，以5摩尔％的负载量，可以很好地合成各种烯丙基酯。该反应的特征在于其高效，广泛的底物范围，优异的位阻耐受性和良好的官能团相容性。