dimethyl cyclohex-3-ene-1,1-dicarboxylate | 41079-58-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: dimethyl cyclohex-3-ene-1,1-dicarboxylate
• CAS: 41079-58-7
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: ULUQSGBQKOTMHC-UHFFFAOYSA-N

物化性质

• 沸点：
  227.0±40.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  tetrafluoroborate of 3-trifluoromethylbenzenediazonium 、 dimethyl cyclohex-3-ene-1,1-dicarboxylate 在 2,6-二叔丁基-4-甲基吡啶 、 palladium(II) trifluoroacetate 、 2,2′-双[(4S)-4-苄基-2-噁唑啉] 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 dimethyl 4-(3-(trifluoromethyl)phenyl)cyclohex-2-ene-1,1-dicarboxylate 、 dimethyl 4-(3-(trifluoromethyl)phenyl)cyclohex-2-ene-1,1-dicarboxylate
  参考文献：
  名称：

  The first examples of the enantioselective Heck–Matsuda reaction: arylation of unactivated cyclic olefins using chiral bisoxazolines

  摘要：

  Successful enantioselective Heck-Matsuda arylations were accomplished for the first time using chiral bisoxazolines as ligands. Enantioselective Heck arylations were performed with several cyclic nonactivated olefins to provide the Heck products in 63-96% isolated yields and in enantiomeric excesses of 54% up to 84%. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.04.079
• 作为产物：
  描述：

  dimethyl 2-but-3-enyl-2-prop-2-enylpropane-1,3-dioate 在 Ru2Cl4(=C=C=CPh2)(PCy3)(η-MeC6H4(Pr-i)4) 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以94%的产率得到dimethyl cyclohex-3-ene-1,1-dicarboxylate
  参考文献：
  名称：

  Coordinatively unsaturated ruthenium allenylidene complexes: highly effective, well defined catalysts for the ring-closure metathesis of α,ω-dienes and dienynes

  摘要：

  定义明确、易于获得且配位不饱和的亚烯基配合物 [RuCl2(CC CPh2)(PCy3)2] 和 [Ru2Cl4(CCCPh2)(PCy3)(Î--MeC6-H4Pri-4)] 是δ、二烯烃和二炔烃的高效催化剂，可方便地高产形成各种官能化的 5、6、7、8、15、16 和 18 分子单环和双环系统。

  DOI：

  10.1039/a900187e

文献信息

• Catalytic asymmetric addition of an amine N–H bond across internal alkenes
  作者：Yumeng Xi、Senjie Ma、John F. Hartwig

  DOI：10.1038/s41586-020-2919-z

  日期：2020.12.10

  direct, enantioselective intermolecular hydroamination of any type of unactivated alkene lacking a directing group occur with only moderate enantioselectivity.10-13 Here we report a cationic iridium system that catalyses intermolecular hydroamination of a range of unactivated, internal alkenes, including those in both acyclic and cyclic alkenes, to afford chiral amines with high enantioselectivity. The

  烯烃的加氢胺化，即在烯烃上添加胺的 NH 键，是一种基本但具有挑战性的有机转化，它从两种丰富的化学原料（烯烃和胺）中产生烷基胺，具有全原子经济性。 1-3 反应特别重要，因为胺，尤其是手性胺，是广泛的天然产物和药物中普遍存在的亚结构。尽管已经致力于开发用于加氢胺化的催化剂，但绝大多数进行分子间加氢胺化的烯烃仅限于共轭、应变或末端烯烃；2-4 只有少数例子是直接添加 NH 键胺在未活化的内部烯烃中的含量，5-7 包括最近的光催化加氢胺化，8，9 和对这些烯烃的对映选择性分子间加成是未知的。事实上，目前对缺乏导向基团的任何类型的未活化烯烃进行直接、对映选择性分子间加氢胺化的实例仅发生中等对映选择性。 10-13 在这里，我们报告了一种阳离子铱系统，该体系催化一系列未活化的内部烯烃的分子间加氢胺化，包括在无环和环状烯烃中的那些，以提供具有高对映选择性的手性胺。该催化剂含有一种新的配体和三氟酰亚胺反阴离子，反应设计包括
• Synthesis of Cembranoid Analogues through Ring-Closing Metathesis of Terpenoid Precursors: A Challenge Regarding Ring-Size Selectivity
  作者：Tanja Heidt、Angelika Baro、Andreas Köhn、Sabine Laschat

  DOI：10.1002/chem.201502051

  日期：2015.8.24

  terpenoids were suitable precursors, despite the presence of competing double bonds in their framework. The size of R and R1 is crucial for successful macrocyclization. Whereas small alkyl substituents at the double bond directed the RCM towards six‐membered ring formation, cross metathesis leading to dimers dominated for bulkier alkyl groups. A similar result was obtained for precursors without functional

  本文描述了使用Grubbs II催化剂对类天麻大环进行开环复分解的系统研究。由香叶醇衍生的三烯和基于溴代烯烃和丙二酸二甲酯的片段制备相对于RCM活性末端在同质位置上具有官能团X且直接连接至另一个末端双键的取代基R，R 1的无环萜烯。尽管它们的骨架中存在竞争性双键，但此类萜类化合物还是合适的前体。R和R 1的大小对于成功实现大环化至关重要。尽管双键上的小烷基取代基将RCM导向六元环形成，但交叉易位导致二聚体占据了更大的烷基基团。对于没有官能团X的前体，获得了相似的结果。在具有不对称的OTBS或OMe基团的不对称取代的萜类前体（R = Et，R 1 = Me）的情况下，可以控制RCM形成大环的类mb体，即具有出色的E选择性分离。通过简化模型底物的量子化学计算进一步研究了取代基的作用。基于这些结果，提出了机械原理。
• Cerium (IV) ammonium nitrate promoted oxidative cyclization of dimethyl 4-pentenylmalonate
  作者：Enrico Baciocchi、Anna Belli Paolobelli、Renzo Ruzziconi

  DOI：10.1016/s0040-4020(01)81235-7

  日期：1992.1

  CAN promoted oxidative cyclization of dimethyl 4-pentenylmalonate has been investigated in MeOH and in AcOH. The product distribution and the regioselectivity of the reaction (5-exo/6-endo ratio) appear to be very sensitive to the reaction conditions as well as the presence and the nature of copper salts, which can also be exploited from the synthetic point of view.

  已经在MeOH和AcOH中研究了CAN促进4-戊烯基丙二酸二甲酯的氧化环化作用。反应的产物分布和区域选择性（5-exo / 6-endo比率）似乎对反应条件以及铜盐的存在和性质非常敏感，这也可以从合成的角度加以利用。看法。
• Solvent effects on manganese(III)-based oxidative free-radical cyclizations: ethanol and acetic acid
  作者：Barry B. Snider、John E. Merritt、Mark A. Dombroski、Brad O. Buckman

  DOI：10.1021/jo00019a014

  日期：1991.9

  Ethanol complements the typical solvent, acetic acid, for Mn(III)-based oxidative free-radical cyclizations. Cyclization of enol ether 1c to give gibberellic acid intermediate 6c is successful in ethanol, but not in acetic acid. Ethanol acts as a reducing agent for primary radicals, converting 13 and 33 to alkanes 17 and 32. Acetylenes can be used as substrates since the vinyl radicals 24 and 25 are reduced by ethanol to alkenes 26-28. The 1-hydroxyethyl radical obtained from ethanol is oxidized to acetaldehyde by Mn(III). The effect of solvent on the oxidative cyclization of unsaturated beta-keto esters 35 and 48 was examined. A higher percentage of 5-exo product is obtained in ethanol. The primary cyclopentanemethyl radicals 40 and 53 are oxidized mainly to alkenes 43 and 57 in ethanol and mainly to the alcohols 42 and 55 and lactones 41 and 58 in acetic acid.
• Ligand, solvent, and deuterium isotope effects in Mn(III)-based oxidative free-radical cyclizations
  作者：Barry B. Snider、Bridget A. McCarthy

  DOI：10.1021/jo00075a015

  日期：1993.11

  Oxidation of beta-keto ester 1 with Mn(Pic)3 and Cu(OAc)2 affords bicycloalkane 8, not the expected alkene 7, which is formed in high yield with Mn(OAc)3 and Cu(OAc)2. A series of control experiments established that the most likely explanation for this observation is that Mn(PiC)2, but not Mn(OAC)2, reacts with the bicyclic radical 5 more rapidly than Cu(OAc)2 does. These studies also indicate the potential for improved yields from oxidative free-radical cyclization of deuterated substrates. For instance, reaction of beta-keto ester 1-d with 2 equiv of Mn(OAc)3 and no Cu(OAC)2 affords 65% of 8, whereas beta-keto ester 1 provides only 22% of 8 under the same conditions. Large kinetic isotope effects change the nature of the termination step and prevent the formation of acyclic radical 3 by intermolecular hydrogen transfer. Solvent and ligand effects on the oxidation of beta-keto ester 1, malonate 14, and acetylenic beta-keto ester 25 are described.