3-acetoxy-5-carbomethoxycyclohex-1-ene | 72359-56-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-acetoxy-5-carbomethoxycyclohex-1-ene
• 英文别名: 3-acetoxy-5-carbomethoxy-1-cyclohexene；Methyl 5-acetyloxycyclohex-3-ene-1-carboxylate
• CAS: 72359-56-9
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: QMTVKLPUNFKWES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 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：

  3-acetoxy-5-carbomethoxycyclohex-1-ene 在 四(三苯基膦)钯 sodium methylate 作用下， 以 甲醇 、 苯 为溶剂， 反应 10.5h， 生成 dimethyl (Z)-(5-carbomethoxy-1-cyclohexen-3-yl)malonate
  参考文献：
  名称：

  Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates. Stereo- and regiochemistry

  摘要：

  DOI：

  10.1021/ja00534a029
• 作为产物：
  描述：

  6-氧杂双环[3.2.1]辛-3-烯-7-酮 在 高氯酸 、 sodium methylate 作用下， 以 水 、 乙酸乙酯 为溶剂， 反应 12.0h， 生成 3-acetoxy-5-carbomethoxycyclohex-1-ene
  参考文献：
  名称：

  Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates. Stereo- and regiochemistry

  摘要：

  DOI：

  10.1021/ja00534a029

文献信息

• Molybdenum catalysts for allylic alkylation
  作者：Barry M. Trost、Mark Lautens

  DOI：10.1021/ja00384a071

  日期：1982.10

  This paper reports on the stoichiometric and catalytic allylic substituion reactions involving molybdenum complexes and the sensitivity of regioselectivity toward the nature of the ligands on molybdenum. Results indicated that the allylic alkylation catalyzed by molybdenum forms a useful and frequently complementary alternative to the palladium-catalyzed reaction. For example, regioselectivity appears

  本文报道了涉及钼配合物的化学计量和催化烯丙基取代反应以及区域选择性对钼配体性质的敏感性。结果表明，由钼催化的烯丙基烷基化形成了钯催化反应的有用且经常互补的替代方案。例如，在 Mo 的情况下，区域选择性似乎对配体变化更敏感。在 ..pi..-allyl 片段的一级碳和二级碳上的连接选择性更高。存在。另一方面，这些反应需要更高的温度和更长的时间。需要对这种钼化学进行更彻底的评估，以描绘其全部潜力。
• [EN] PALLADIUM CATALYZED ADDITION OF AMINES TO 3,4-EPOXY-1-BUTENE<br/>[FR] ADDITION D'AMINES, CATALYSEE PAR PALLADIUM, A 3,4-EPOXY-1-BUTENE
  申请人：EASTMAN CHEMICAL COMPANY

  公开号：WO1993025516A1

  公开（公告）日：1993-12-23

  (EN) 4-amino-2-buten-1-ol is formed by the regioselective addition of primary amines to 3,4-epoxy-1-butene. A quantity of the primary amine is reacted with 3,4-epoxy-1-butene in a reaction medium in the presence of a catalyst. The reaction medium is a liquid which has an ET(30) no less than about 32. The catalyst is a complex of palladium and phosphine ligands. A method of forming 4-amino-2-buten-1-ol using 3,4-epoxy-1-butene is disclosed. A nitrogen nucleophile (e.g., an amine) is reacted with 3,4-epoxy-1-butene in the presene of a polymer-bound complex of palladium having up to four phosphine ligands.(FR) Du 4-amino-2-buten-1-ol, est formé par l'addition régiosélective d'amines primaires à du 3,4-époxy-1-butène. Une certaine quantité de l'amine primaire est mise en réaction avec du 3,4-époxy-1-butène dans un milieu de réaction et en présene d'un catalyseur. Le milieu de réaction est un liquide présentant une énergie de transition ET (30), égale ou supérieure à 32 environ. Le catalyseur est un complexe de palladium et de ligands de phosphine. Un procédé de production de 4-amino-2-buten-1-ol à partir de 3,4-époxy-1-butène est décrit. Un agent nucléophile à azote (tel qu'une amine), est mis en réaction avec du 3,4-époxy-1-butène en présence d'un complexe lié par polymère d'un palladium contenant jusqu'à quatre ligands de phosphine.

  4-氨基-2-酮-1-醇（4-amino-2-buten-1-ol）是由选择性加成的原烷胺与3,4-氧杂环-1-丁烯反应形成的。一定量的原烷胺与3,4-氧杂环-1-丁烯在含有催化的反应介质中反应。该反应介质是一种液态物质，其ET(30)值不低于约32。该催化的复合物是钯与磷配位体。对4-氨基-2-酮-1-醇的合成方法，从3,4-氧杂环-1-丁烯提供了如下表述。作为氮核苷酸（例如胺）与聚合化的钯复合物在3,4-氧杂环-1-丁烯的环境下反应，某一数量的原烷胺。
• Allylstannanes as electrofugal partners in allylic alkylation
  作者：Barry M. Trost、Ehud Keinan

  DOI：10.1016/s0040-4039(00)92814-4

  日期：1980.1
• Lipase−Silicone Biocomposites:  Efficient and Versatile Immobilized Biocatalysts
  作者：Iqbal Gill、Eitel Pastor、Antonio Ballesteros

  DOI：10.1021/ja9924849

  日期：1999.10.1

  The last few decades have seen an explosion in the application of enzymes to organic chemistry, as these biological catalysts have continued to demonstrate their unique synthetic capabilities. Despite this, a key prerequisite for establishing enzymes as standard reagents in synthetic chemistry, specifically the availability of generic technologies providing inexpensive, robust, and reusable heterogeneous biological catalysts, still remains to be fulfilled. Herein, we describe a novel and hi,ghly efficient immobilization methodology for one of the most utilitarian classes of biocatalysts, namely, lipases. The procedure is based upon the adsorption of crude and pure Lipases onto poly(hydroxymethylsiloxane), followed by the incorporation of the formed adsorbates into room-temperature vulcanizable silicones, to form biocatalytic composites. This provides hyperactivated catalysts showing activity enhancements of up to 54-fold as compared with the native enzymes, catalytic densities of up to several hundred kilo-units per gram of immobilizate, and high operational activity and stability in aqueous and organic media. The flexibility of silicone polymer chemistry enables the catalytic biocomposites to be prepared with a variety of physicochemistries, and to be fabricated as solid monoliths, sheets of thick films, particulates, and solid foams, thereby allowing the production of tailored catalysts for a variety of applications. The production and properties of a range of lipase-silicone composites are discussed, and the extended performances of selected catalysts are compared with those of the free enzymes and commercial heterogeneous biocatalysts in model synthetic reactions.
• Asymmetric allylic alkylation catalyzed by palladium-sparteine complexes
  作者：Antonio Togni

  DOI：10.1016/s0957-4166(00)86122-4

  日期：1991.1

  The cationic complex [Pd(eta-3-C3H5)(sparteine)]PF6 (6) was found to be a suitable catalyst precursor for the asymmetric alkylation of allylic acetates with Na[CH(COOMe)2] as the nucleophile. This constitutes one of the first and still rare examples of a phosphine-free system for this type of Pd-catalyzed reaction. Using 5 mol % of 6, alkylation products were obtained in up to 90 % isolated yield and 85 % enantiomeric excess. The alkylation reaction was shown to occur with overall retention of configuration, indicating an analogous mechanism to the one previously proposed for phosphine-containing catalysts. The reactivity of allylic acetates is strongly dependent upon the nature of the substituents, open-chain aliphatic substrates being unreactive.