(E)-2-甲基-4-苯基-3-丁烯酸甲酯 | 33599-85-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (E)-2-甲基-4-苯基-3-丁烯酸甲酯
• 英文名称: (E)-2-methyl-4-phenyl-3-butenoic acid methyl ester
• 英文别名: (+/-)-methyl 2-methyl-trans-styrylacetate；methyl (E)-2-methyl-4-phenylbut-3-enoate；methyl 2-methyl-4-phenyl-3-butenoate；methyl 2-methyl-4-phenylbut-3-enoate；methyl (E)-4-phenylbut-3-en-1-oate；Methyl-trans-2-methyl-4-phenyl-3-butenoat
• CAS: 33599-85-8
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: KPZBEVBLJYUANV-CMDGGOBGSA-N

物化性质

• 沸点：
  287.4±19.0 °C(Predicted)
• 密度：
  1.035±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-2-甲基-4-苯基-3-丁烯酸甲酯 在 sodium azide 、 phosphate buffer 作用下， 以 乙醚 、 水 为溶剂， 反应 120.08h， 生成 methyl (S,E)-2-methyl-4-phenylbut-3-enoate
  参考文献：
  名称：

  Total Synthesis of Cryptophycins via a Chemoenzymatic Approach

  摘要：

  A highly convergent synthesis of cryptophycins in their enantiomerically-pure forms was achieved. Our strategy consists of the synthesis of the two units 3 and 4 and linking them together to form the macrocyclic ring. The upper unit 3 was prepared from 10 in four steps, and the lower unit 4 was prepared from 20 in three steps. Enantioselective biocatalytic methodology was used to prepare the requisite chiral building blocks, (R)-11 and (R)-19. The stereochemical versatility of this synthetic approach is demonstrated by the synthesis of cryptophycin A and the four diastereomers of cryptophycin C.

  DOI：

  10.1021/jo960972i
• 作为产物：
  描述：

  2-Methyl-4-phenyl-3-tosylbutanoic acid 在 盐酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 生成 (E)-2-甲基-4-苯基-3-丁烯酸甲酯
  参考文献：
  名称：

  Lithium 3-Lithio-3-tosylalkanoates: .beta.-Acylvinyl Anion Equivalents of .beta.-Lithiated .alpha.,.beta.-Unsaturated Carboxylic Acids

  摘要：

  The dilithiation of beta-tosylated propanoic, 2-methylpropanoic, and butanoic acid 10 with n-butyllithium at -78 degrees C leads to the corresponding lithium 3-lithio-3-tosylalkanoates 11. They react with different electrophilic reagents (deuterium oxide, iodine, trimethylchlorosilane, alkyl halides, and acyl chlorides) to give the corresponding 3-substituted tosylated alkanoic acids 12. When carbonyl compounds are allowed to react with intermediates 11 followed by in situ lactonization with trifluoracetic anhydride and base-promoted elimination alpha,beta-butenolides are obtained. This methodology is applied to the direct synthesis of the rosefuran lactone precursor 14cg, the O-benzyl derivative of (+/-)-umbelactone (14ch), and (+/-)-andirolactone (14ci). The alkylation and acylation reactions of organolithium compounds 11 followed by esterification with hydrogen chloride in methanol and treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afford alpha,beta- and/or beta,gamma-unsaturated esters 17 and/or 18 and unsaturated 4-keto esters 19, respectively. The last methodology has been applied to the synthesis of the unsaturated 4-keto ester 19ae precursor of the seco acid of (+/-)-pyrenophorin (22).

  DOI：

  10.1021/jo00090a043

文献信息

• Visible Light Induced Brønsted Acid Assisted Pd‐Catalyzed Alkyl Heck Reaction of Diazo Compounds and <i>N</i> ‐Tosylhydrazones
  作者：Ziyan Zhang、Nikita Kvasovs、Anastasiia Dubrovina、Vladimir Gevorgyan

  DOI：10.1002/anie.202110924

  日期：2022.1.3

  mild visible light-induced palladium-catalyzed alkyl Heck reaction of diazo compounds and N-tosylhydrazones is reported. This method features Brønsted acid assisted generation of hybrid palladium C(sp3)-centered radical intermediate and broad reaction scope, highlighting the diverse applicability and the potential utility of this protocol in late-stage functionalization.

  报道了重氮化合物和N-甲苯磺酰腙的温和可见光诱导的钯催化烷基 Heck 反应。该方法具有布朗斯台德酸辅助生成杂化钯C(sp 3 )中心自由基中间体和广泛的反应范围，突出了该方案在后期功能化中的多样化适用性和潜在效用。
• Diastereoselective epoxidation of allylically substituted alkenes using metalloporphyrin catalysts
  申请人：Che Chi-Ming

  公开号：US20050209470A1

  公开（公告）日：2005-09-22

  Diastereoselective epoxidation of allylically substituted alkenes using metalloporphyrins as catalyst provides high trans-selectivities (i.e., trans-:cis-epoxide ratio). A diversity of cycloalkenes bearing different allylic substituents are shown to be efficiently epoxidized to afford the corresponding trans-epoxides with excellent trans-selectivities (up to >98%) and good yields (up to 99%). Acyclic allylic alkenes bearing different allylic substituents are efficiently epoxidized to afford the corresponding erythro-epoxides with good erythro-selectivities. The metalloporphyrin-catalyzed reactions exhibit up to 20 times higher trans-selectivities than the conventional method using m-chloroperoxybenzoic acid as oxidant.

  使用金属卟啉作为催化剂的烯丙基取代烯烃的非对映选择性环氧化反应提供高选择性（即反式：顺式环氧化物比）。显示出带有不同烯丙基取代基的多样环烯烃能够有效地环氧化，产生相应的反式环氧化物，具有优异的反式选择性（高达>98%）和良好的产率（高达99%）。带有不同烯丙基取代基的无环烯丙基烯烃能够有效地环氧化，产生相应的顺式环氧化物，具有良好的顺式选择性。金属卟啉催化的反应显示出比使用m-氯过氧苯甲酸作为氧化剂的传统方法高达20倍的反式选择性。
• Metalloporphyrin-Catalyzed Diastereoselective Epoxidation of Allyl-Substituted Alkenes
  作者：Wing-Kei Chan、Man-Kin Wong、Chi-Ming Che

  DOI：10.1021/jo047733c

  日期：2005.5.1

  developed an efficient method for erythro-selective epoxidation of acyclic allyl-substituted alkenes, including allylic alcohols, amines, and esters. Up to 9:1 erythro selectivities for terminal allyllic alkenes could be achieved, which are significantly higher than that achieved using m-CPBA as an oxidant. In addition, the synthetic utilities of this epoxidation method were highlighted in stereoselective synthesis

  通过使用[Mn（2,6-Cl 2 TPP）Cl]（1）作为催化剂，Oxone / H 2 O 2作为氧化剂，我们开发了一种有效的方法，用于无环烯丙基取代的烯烃的赤型选择性环氧化，包括烯丙醇，胺和酯。末端烯丙基烯烃可达到9：1的赤型选择性，这明显高于使用m -CPBA作为氧化剂所达到的选择性。此外，这种环氧化方法的合成效用在关键的抗HIV药物中间体的立体选择性合成和糖基的环氧化中得到了强调。
• The Codimerizations of Styrene with Vinyl Compounds Catalyzed by Olefin-palladium(II) Chloride Complexes
  作者：Keiji Kawamoto、Atsushi Tatani、Toshinobu Imanaka、Shiichiro Teranishi

  DOI：10.1246/bcsj.44.1239

  日期：1971.5

  codimerizations of styrene with vinyl acetate and with methyl vinyl ketone gave 50% codimer and 125% codimers respectively. When nitroethylene and n-butyl vinyl ether were used as the vinyl compound, no codimers were formed. The codimerization of styrene-d3 with ethylene was also carried out. The reaction mechanism involving the five-coordinate hydridopalladiumolefin intermediate was proposed and discussed in

  在温和条件下，在均相体系中研究了由二-μ-氯-二氯双（苯乙烯）二钯（II）（Pd（C6H5CH=CH2）Cl2）2 催化的苯乙烯与乙烯基化合物的共二聚反应。苯乙烯和丙烯酸甲酯的反应在 50°C 下进行 6 小时，以使用的钯 (II) 计，产生 220% 的共二聚体、169% 的丙烯酸甲酯二聚体和 18% 的苯乙烯二聚体。苯乙烯与乙酸乙烯酯和甲基乙烯基酮的共二聚反应分别得到 50% 和 125% 的共二聚体。当硝基乙烯和正丁基乙烯基醚用作乙烯基化合物时，没有形成共二聚体。还进行了苯乙烯-d3与乙烯的共二聚。
• Nickel-Catalyzed Reductive Cross-Coupling of Oxalates Derived from α-Hydroxy Carbonyls with Vinyl Bromides
  作者：Fan Wu、Cheng Ye、Weiqi Tong

  DOI：10.1055/s-0040-1719881

  日期：2022.5

  A nickel-catalyzed cross-electrophile coupling is disclosed in which a range of vinyl bromides were utilized as electrophiles with oxalates derived from α-hydroxy carbonyls as precursors to carbonyl radical coupling partners. This method is compatible with a broad range of functional groups, providing a complementary solution for the construction of β,γ-unsaturated carbonyl compounds.

  公开了一种镍催化的交叉亲电偶联物，其中使用了一系列溴乙烯作为亲电试剂，其中衍生自 α-羟基羰基的草酸盐作为羰基自由基偶联配偶体的前体。该方法与广泛的官能团兼容，为构建 β,γ-不饱和羰基化合物提供了补充解决方案。