methyl 4-phenyl-2-(tosylimino)but-3-enoate | 1451010-25-5

• 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: methyl 4-phenyl-2-(tosylimino)but-3-enoate
• CAS: 1451010-25-5
• 化学式: C₁₈H₁₇NO₄S
• 分子量: 343.403
• InChiKey: WFTCRQFDMOSPSS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  72.8
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl 4-phenyl-2-(tosylimino)but-3-enoate 在 dirhodium tetraacetate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 copper dichloride 作用下， 以 二氯甲烷 为溶剂， 反应 74.17h， 生成 dimethyl (Z)-5-hydroxy-2-((4-methylphenyl)sulfonamido)-4,5-diphenylhex-2-enedioate
  参考文献：
  名称：

  Regio- and Diastereoselective Construction of α-Hydroxy-δ-amino Ester Derivatives via 1,4-Conjugate Addition of β,γ-Unsaturated N-Sulfonylimines

  摘要：

  A first example of 1,4-conjugate addition of beta,gamma-unsaturated N-sulfonylimines via the oxonium ylides trapping process was developed. This method afforded a novel and efficient access for the high regio- and diastereoselective construction of alpha-hydroxyl-delta-amino esters derivatives, which exhibit inhibitory activity on PTP1B and SIRT1 enzymes in vitro. The synthetic potentials and the biological activity of the resulting products were well demonstrated to be promising for drug discovery.

  DOI：

  10.1021/jo500176g
• 作为产物：
  描述：

  methyl 4-phenyl-2-oxo-3-butenoate 、 对甲苯磺酰胺 在 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 methyl 4-phenyl-2-(tosylimino)but-3-enoate
  参考文献：
  名称：

  双官能尿素/ Hg（OAc）2介导的二硫代丙二酸酯和β，γ-不饱和α-酮基酯合成4-芳基-6-氧羰基-2-吡喃酮和2-吡啶酮

  摘要：

  通过双功能尿素催化的迈克尔加成/内酰胺化或内酰胺化，然后进行Hg（OAc）2-或Hg（OAc）2 / DBU介导的水解/脱羧/脱氢过程，获得双取代的2-吡喃酮和2-吡啶酮。这种一锅两步的操作方案可以在温和的反应条件下，以实际收率从二硫代丙二酸酯和β，γ-不饱和α-酮酸酯快速合成4,6-二取代的2-吡喃酮和2-吡啶酮。另外，将获得的2-吡啶酮以优异的产率容易地转化为2,4,6-三取代的吡啶。

  DOI：

  10.1021/acs.joc.1c00323

文献信息

• Tuning Electronic and Steric Effects: Highly Enantioselective [4+1] Pyrroline Annulation of Sulfur Ylides with α,β-Unsaturated Imines
  作者：Liang-Qiu Lu、Ji-Ji Zhang、Fang Li、Ying Cheng、Jing An、Jia-Rong Chen、Wen-Jing Xiao

  DOI：10.1002/anie.201000755

  日期：2010.6.14

  A change in tune: A novel [4+1] annulation between atropisomeric sulfur ylides 1 and unsaturated imines 2 was developed. The method allows the synthesis of enantioenriched pyrroline products 3 in high yield and with excellent stereocontrol. The origin of stereoinduction was primarily rationalized by a conformational analysis of the ylides.

  音调变化：开发了一种新的[4 + 1]环锭异构硫基亚砜1和不饱和亚胺2之间的环。该方法允许高收率和优异的立体控制合成富含对映体的吡咯啉产物3。立体诱导的起源主要是通过对叶立德进行构象分析来合理化的。
• Enantioselective [3 + 2] annulation of α-substituted allenoates with β,γ-unsaturated <i>N</i>-sulfonylimines catalyzed by a bifunctional dipeptide phosphine
  作者：Huanzhen Ni、Weijun Yao、Yixin Lu

  DOI：10.3762/bjoc.12.37

  日期：——

  The first enantioselective [3 + 2] annulation of alpha-substituted allenoates with beta,gamma-unsaturated N-sulfonylimines is described. In the presence of a dipeptide phosphine catalyst, a wide range of highly functionalized cyclopentenes bearing an all-carbon quaternary center were obtained in moderate to good yields and with good to excellent enantioselectivities.

  描述了α-取代的烯酸酯与β，γ-不饱和N-磺酰亚胺的第一次对映选择性[3 + 2]环。在二肽膦催化剂的存在下，以中等至良好的产率以及良好至优异的对映选择性获得了带有全碳季中心的多种高度官能化的环戊烯。
• E,Z-Stereodivergent synthesis of N-tosyl α,β-dehydroamino esters via a Mukaiyama–Michael addition
  作者：Miguel Espinosa、Andrea García-Ortiz、Gonzalo Blay、Luz Cardona、M. Carmen Muñoz、José R. Pedro

  DOI：10.1039/c5ra27354d

  日期：——

  The stereodivergent synthesis of N-tosyl α,β-dehydroamino esters via a Mukaiyama–Michael addition is reported. The reaction of silylketene acetals with N-tosylimines derived from β,γ-unsaturated α-keto esters in dichloromethane provided the corresponding (Z)-α,β-dehydroamino esters while the (E)-isomers were obtained when the reaction was carried out in the presence of 10 mol% copper(II) triflate.

  据报道，通过Mukaiyama-Michael加成立体合成N-甲苯磺酰基α，β-脱氢氨基酯。甲硅烷基乙烯酮缩醛与β，γ-不饱和α-酮酸酯衍生的N-甲苯磺胺在二氯甲烷中的反应提供了相应的（Z）-α，β-脱氢氨基酯，而在进行反应时获得了（E）-异构体在10mol％的三氟甲磺酸铜（II）存在下。
• Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to β,γ-unsaturated α-ketimino esters
  作者：Miguel Espinosa、Gonzalo Blay、Luz Cardona、Isabel Fernández、M. Carmen Muñoz、Jose R. Pedro

  DOI：10.1080/00958972.2018.1437422

  日期：2018.3.19

  Abstract In this paper, we report the application of chiral complexes of La(III) with pyBOX ligands as Lewis acid catalysts in the conjugate addition of malonic esters to N-tosyl imines derived from β,γ-unsaturated α-keto esters to give the corresponding chiral α,β-dehydroamino esters. pyBOX complexes with La(III), Yb(III), Sc(III), and In(III) triflates were assessed in this reaction but only La(III)

  摘要 在本文中，我们报道了 La(III) 与 pyBOX 配体的手性配合物作为路易斯酸催化剂在丙二酸酯与 β,γ-不饱和 α-酮酯衍生的 N-甲苯磺酰亚胺的共轭加成中的应用。相应的手性α,β-脱氢氨基酯。在该反应中评估了与 La(III)、Yb(III)、Sc(III) 和 In(III) 三氟甲磺酸盐的 pyBOX 配合物，但只有 La(III) 表现出良好的活性和对映选择性，而 Yb(III) 提供了预期的产物收率和立体选择性低，Sc(III) 和 In(III) 配合物完全失活。La(OTf)3 与原位制备的二苯基-pyBOX 配体的复合物提供了最好的结果，并允许以优异的产率获得手性 α,β-脱氢氨基酯 3，E:Z 非对映体比率 (29:71–99:1)和高对映体过量（20-95%）。尽管芳环上吸电子基团的存在不利于立体选择性，但该反应可应用于具有取代的芳环或杂环连接到双键的亚胺。
• Phosphine-catalyzed [3+2] annulation of α-substituted allenoates with ester-activated α,β-unsaturated imines: a novel variation of the Lu [3+2] cycloaddition reaction
  作者：Junjun Tian、Zhengjie He

  DOI：10.1039/c3cc38264h

  日期：——

  A phosphine-catalyzed [3+2] annulation reaction of alpha-substituted allenoates with ester-activated alpha,beta-unsaturated imines is reported, which provides new and efficient access to highly functionalized cyclopentenes bearing one all-carbon quaternary center. This reaction also expands the scope of the famous Lu [3+2] cycloaddition reaction.

  报道了一种膦催化的α-取代的烯酸酯与酯活化的α，β-不饱和亚胺的膦酸酯化的[3 + 2]环化反应，它为具有一个全碳四元中心的高度官能化的环戊烯提供了新的有效途径。该反应还扩大了著名的Lu [3 + 2]环加成反应的范围。