2-乙酰基戊-4-烯酸甲酯 | 3897-04-9

• 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
• 中文名称: 2-乙酰基戊-4-烯酸甲酯
• 英文名称: methyl 2-acetylpent-4-enoate
• 英文别名: 4-Pentenoic acid, 2-acetyl-, methyl ester
• CAS: 3897-04-9
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: ZPODYHCGBAQQKD-UHFFFAOYSA-N

物化性质

• 沸点：
  104-109 °C(Press: 4 Torr)
• 密度：
  1.0178 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2918300090

反应信息

• 作为反应物：
  描述：

  2-乙酰基戊-4-烯酸甲酯 以 sodium hydroxide 、 硫酸 为溶剂， 生成 5-已烯-2-酮
  参考文献：
  名称：

  跨复分解路线的功能化的α-甲基α-取代的氨基酸

  摘要：

  用化学酶方法合成功能化的α-甲基α-取代的氨基酸。这涉及酰胺酶介导的α-甲基α-取代的侧链ω-不饱和氨基酸的酶促拆分，然后通过交叉复分解进行功能化。

  DOI：

  10.1002/adsc.200600446
• 作为产物：
  描述：

  乙酰乙酸甲酯 、 3-溴丙烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以54%的产率得到2-乙酰基戊-4-烯酸甲酯
  参考文献：
  名称：

  一种简便的全合成拟松香酸A的方法

  摘要：

  从市售起始原料开始的16个步骤中完成了天然产物假Laric酸A（1）的立体选择性全合成的新策略，该方法具有二碘化sa（SmI 2）介导的分子内烯烃-酮基自由基环化和闭环易位的作用（RCM）反应，以立体选择性地铸造了伪拉来酸A（1）的不寻常的反式[5-7]-双环核。

  DOI：

  10.1021/ol200741j

文献信息

• Nickel-Catalyzed Alkyl–Alkyl Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for the Synthesis of Alkylcyclopropanes
  作者：Amberly B. Sanford、Taylor A. Thane、Tristan M. McGinnis、Pan-Pan Chen、Xin Hong、Elizabeth R. Jarvo

  DOI：10.1021/jacs.0c01330

  日期：2020.3.18

  3-diol derivatives. Notably, this transformation is utilized to synthesize a range of mono- and 1,2-disubstituted alkylcyclopropanes, including those derived from terpenes, steroids, and aldol products. Additionally, enantioenriched cyclopropanes are synthesized from the products of proline-catalyzed and Evans aldol reactions. A procedure for direct transformation of 1,3-diols to cyclopropanes is also

  两个 Csp3-X 键的交叉亲电偶联反应仍然具有挑战性。在此，我们报告了分子内镍催化的 1,3-二醇衍生物的交叉亲电偶联反应。值得注意的是，这种转化用于合成一系列单和 1,2-二取代的烷基环丙烷，包括衍生自萜烯、类固醇和醛醇产品的那些。此外，对映体富集的环丙烷是由脯氨酸催化和埃文斯羟醛反应的产物合成的。还描述了将 1,3-二醇直接转化为环丙烷的过程。计算和实验数据与镍催化机制一致，该机制始于二级中心的立体氧化加成。
• Mn(III)-based oxidative free-radical cyclizations of γ,γ-bis(allylic) acetoacetates
  作者：Mark A. Dombroski、Barry B. Snider

  DOI：10.1016/s0040-4020(01)92231-8

  日期：1992.2

  Oxidative free-radical cyclizations of γ,γ-(bis)allylic acetoacetates demonstrate that 1,1-disubstituted double bonds are much more reactive than mono- or chloroalkyl-substituted double bonds. The product isolated suggests that bicyclo[3.2.1]octanes 25, 33 and 36 are formed from boat cyclohexyl radical 42 and tandem cyclization products 30, 37 and 38 are obtained from boat cyclohexyl radical 41.

  γ，γ-（双）烯丙基乙酰乙酸酯的氧化自由基环化表明1,1-二取代的双键比单或氯烷基取代的双键更具反应性。分离的产物表明，双环[3.2.1]辛烷25，33和36是从船环己基形成42个串联环化产物30，37和38是从船环己基得到41。
• Substituted (aryl, heteroaryl, arylmethyl or heteroarylmethyl)
  申请人：Rhone-Poulenc Rorer Pharmaceuticals Inc.

  公开号：US06057369A1

  公开（公告）日：2000-05-02

  This invention is directed to compounds of formula I: ##STR1## wherein the variables are as described herein. Compounds within the scope of the present invention possess useful properties, more particularly pharmaceutical properties. They are especially useful for inhibiting the production or physiological effects of TNF in the treatment of a patient suffering from a disease state associated with a physiologically detrimental excess of tumor necrosis factor (TNF). Compounds within the scope of the present invention also inhibit cyclic AMP phosphodiesterase, and are useful in treating a disease state associated with pathological conditions that are modulated by inhibiting cyclic AMP phosphodiesterase, such disease states including inflammatory and autoimmune diseases, in particular type IV cyclic AMP phosphodiesterase. Compounds within the scope of the present invention may also inhibit an MMP, and are useful in treating a disease state associated with pathological conditions that are modulated by inhibiting MMPs, such disease states involve tissue breakdown and those associated with a physiologically detrimental excess of TNF. The present invention is therefore also directed to the pharmaceutical use of the compounds, pharmaceutical compositions containing the compounds, intermediates leading thereto and methods for the preparation of the compounds and their intermediates.

  这项发明涉及到式I的化合物：##STR1## 其中变量如本文所述。本发明范围内的化合物具有有用的性质，更具体地说是药用性质。它们特别适用于抑制TNF的产生或生理效应，用于治疗患有与生理上有害的肿瘤坏死因子（TNF）过量相关的疾病状态的患者。本发明范围内的化合物还抑制环状AMP磷酸二酯酶，并且适用于治疗与通过抑制环状AMP磷酸二酯酶调节的病理条件相关的疾病状态，这些疾病状态包括炎症和自身免疫疾病，特别是第四型环状AMP磷酸二酯酶。本发明范围内的化合物还可能抑制MMP，并且适用于治疗与通过抑制MMPs调节的病理条件相关的疾病状态，这些疾病状态涉及组织分解以及与生理上有害的TNF过量相关的疾病状态。因此，本发明还涉及化合物的药用，含有该化合物的药物组合物，导致该化合物的中间体以及该化合物及其中间体的制备方法。
• Manganese (III) based oxidative free-radical annulations
  作者：Barry B. Snider、Brad O. Buckman

  DOI：10.1016/s0040-4020(01)89163-8

  日期：——

  of diethyl allylmalonate (6b), sterically nucleophilic alkenes, Mn(OAc)3·2H2O and Cu(OAc)2·H2O gives methylenecyclopentanes 13 to 17 in 17–100% yield by an oxidative free-radical annulation. Similarly, oxidative annulation of diethyl crotylmalonate and ethyl benzylacetoacetate with an alkene gives vinylcyclopentane (30) and tetralin (35).

  烯丙基丙二酸二乙酯（6b），空间亲核烯烃Mn（OAc）3 ·2H 2 O和Cu（OAc）2 ·H 2 O的反应通过氧化自由基环化反应以17-100％的收率得到亚甲基环戊烷13至17。类似地，巴豆丙二酸二乙酯和苄基乙酰乙酸乙酯与烯烃的氧化环化得到乙烯基环戊烷（30）和四氢化萘（35）。
• Palladium- and cobalt-mediated cyclisations of halo-polyenes: a comparative study
  作者：Amjad Ali、G. Bryon Gill、Gerald Pattenden、Graeme A. Roan、Toh-Seok Kam

  DOI：10.1039/p19960001081

  日期：——

  Cobalt(I)-mediated mono- and bi-cyclisations of halo-polyenes are compared and contrasted with corresponding reactions using the Heck reaction. The procedures are found to complement one another, with each having advantages and disadvantages, in the cases studied. Thus, treatment of the vinyl iodide 1 under Heck conditions led to the novel 1,3-diene 3 in 93% yield, whereas reaction between 1 and cobalt(I) salophen resulted in the formation of the organocobalt complex 4 (∼50%) as black crystals. Subsequent irradiation of 4 then led to the 6,5-ring fused bicycle 5 in 85% yield. In similar fashion, a Heck reaction with the analogous vinyl iodide 8 produced the product 9 of 6-ring cyclisation followed by β-hydride elimination, whereas the corresponding cobalt-mediated reaction with 8 led to the new organocobalt 10 albeit in only low yield (∼20%). In reactions akin to those studied by Overman et al., Heck reaction with the dienyl aryl iodide 14 was shown to lead to a mixture of the bicycle 16 and the tricycle 17 in a 1:1 ratio. By contrast treatment of 14 with cobalt(I) salophen produced largely the tetralin 18. The iodo-diene 33 gave rise to the spirocycle 35 under Heck reaction conditions, and the related spirocycle 42 was produced from the bromo-acetal 40 via 41, using cobalt(I) mediated reactions.

  钴(I)介导的卤代多烯的单环化和双环化与相应的Heck反应进行了比较和对比。研究发现这些方法互为补充，各有优缺点，在所研究的案例中均适用。因此，在Heck条件下将乙烯基碘1处理后，得到了新型1,3-二烯3，产率为93%；而将1与钴(I)水杨酮反应则生成了有机钴配合物4（约50%），呈黑色晶体。随后对4进行辐照处理，得到了6,5-双环5，产率为85%。类似地，与类似的乙烯基碘8进行Heck反应，得到6-环化产物9，随后发生β-氢消除反应；而与8进行相应的钴介导反应，则得到了新的有机钴10，尽管产率较低（约20%）。在与Overman等人研究的反应类似的情况下，向二烯基芳基碘14进行Heck反应，得到了16和17的双环和三环混合物，比例为1:1。相比之下，将14与钴(I)水杨酮反应，则主要得到了四氢萘18。碘代二烯33在Heck反应条件下生成了螺环35，而通过钴(I)介导反应从溴代缩醛40经过41生成了相关螺环42。