then-2-ylideneacetoacetic acid ethyl ester | 59155-60-1

• 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: then-2-ylideneacetoacetic acid ethyl ester
• 英文别名: (2-Thenylidene)acetoacetic acid ethyl ester；ethyl 3-oxo-5-thiophen-2-ylpent-4-enoate
• CAS: 59155-60-1
• 化学式: C₁₁H₁₂O₃S
• 分子量: 224.28
• InChiKey: BXYIOWQWTUHLMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  71.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  then-2-ylideneacetoacetic acid ethyl ester 、 乙基2-咪唑烷基亚基乙酸酯 以 乙醇 为溶剂， 反应 6.0h， 以yields 5-methyl-7-(then-2-yl)-1,2,3,7-tetrahydroimidazolo[1,2-a]pyridine-6,8-dicarboxylic acid diethyl ester of melting point 134°C (ethanol)的产率得到5-methyl-7-(then-2-yl)-1,2,3,7-tetrahydroimidazolo[1,2-a]pyridine-6,8-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Tetrahydroimidazolo[1,2-a]pyridine derivatives

  摘要：

  3-和5-位带有羰基功能的1,4-二氢吡啶，6-位可选择性地被低碳基取代，4-位被低碳基、苯基、取代苯基或杂环基所取代，并通过1-和2-位融合到五、六或七元环烷基环上，其中一个亚甲基可以被硫、氧、亚氨基或烷基亚氨基所取代，是抗高血压药和冠状血管扩张剂。这些化合物，其中6-甲基-4-(3-硝基苯基)-1,2-戊亚甲基-1,4-二氢吡啶-3,5-二羧酸3,5-二乙酯是一个代表性实施例，是通过酰乙酰酸酯和环状烯氨酮羰基衍生物的缩合制备的。

  公开号：

  US03935220A1

文献信息

• Asymmetric Organocatalytic [4 + 1] Annulations: Enantioselective Construction of Multifunctionalized Spirocyclopentane Oxindoles Bearing α,α-Disubstituted α-Amino-β-keto Esters
  作者：Chuan-Chuan Wang、Jian Huang、Xin-Hao Li、Søren Kramer、Guo-Qiang Lin、Xing-Wen Sun

  DOI：10.1021/acs.orglett.8b00927

  日期：2018.5.18

  α-disubstituted α-amino-β-keto esters was achieved through [4 + 1] annulation of oxindoles and α-imine-β-oxo-γ,δ-unsaturated esters under mild conditions in good yields (up to 82%) and stereoselectivities (up to >20:1 dr, 96% ee). The reaction is amenable to gram scale synthesis using catalyst loading as low as 1 mol %. The corresponding chiral α,α-disubstituted α-amino-β-keto esters could be easily transformed

  通过在温和的条件下，于[4 +1]环化吲哚和α-亚胺-β-氧代-γ，δ-不饱和酯，可以实现具有α，α-二取代的α-氨基-β-酮基酯的螺硫辛酯的高对映选择性。良率（高达82％）和立体选择性（高达> 20：1 dr，96％ee）。该反应适合于使用低至1mol％的催化剂负载进行克规模的合成。相应的手性α，α-二取代的α-氨基-β-酮基酯可以很容易地转化为环戊[ b ]吲哚衍生物，而不会破坏对映体纯度。
• Asymmetric Organocatalytic [4 + 1] Annulations Involving a Polarity Reversal Process: A Tandem Catalytic Approach to Highly Functionalized Spiropyrazolone Derivatives
  作者：Chang-Yin Tan、Hong Lu、Jia-Lu Zhang、Jin-Yu Liu、Peng-Fei Xu

  DOI：10.1021/acs.joc.9b02684

  日期：2020.1.17

  A tandem catalytic strategy for the asymmetric synthesis of spirocyclopentanone pyrazolones bearing three contiguous stereocenters and two quaternary carbons with good stereoselectivities has been developed. This strategy, using pyrazolones as efficient C1 synthons and involving a polarity reversal process, not only overcame the energy barrier of the dearomatization process but also avoided nucleophilic

  已开发了一种串联催化策略，用于不对称合成螺环戊酮吡唑啉酮，其具有三个连续的立体中心和两个具有良好立体选择性的季碳。这种使用吡唑啉酮作为有效的C1合成子并涉及极性反转过程的策略，不仅克服了脱芳香化过程的能垒，而且避免了烯醇互变异构体中羟基的亲核加成。此外，可用Lawesson试剂将螺环戊酮转化为螺环己酰胺吡唑啉酮。
• Multiple Hydrogen-Bonding Bifunctional Thiourea-Catalyzed Asymmetric Dearomative [4 + 2] Annulation of 3-Nitroindoles: Highly Enantioselective Access to Hydrocarbazole Skeletons
  作者：Deng-Feng Yue、Jian-Qiang Zhao、Xiao-Zhen Chen、Yan Zhou、Xiao-Mei Zhang、Xiao-Ying Xu、Wei-Cheng Yuan

  DOI：10.1021/acs.orglett.7b02068

  日期：2017.9.1

  A method for the enantioselective construction of hydrocarbazole skeletons through dearomative [4 + 2] annulation of 3-nitroindoles with Nazarov reagents is reported. The reactions use multiple hydrogen-bonding bifunctional thiourea as catalyst and are highly diastereo- and enantioselective (up to >20:1 dr and >99% ee). The protocol was demonstrated by preparative-scale experiment and the versatile

  报道了一种通过使用Nazarov试剂将3-硝基吲哚脱芳香性[4 + 2]脱环而对羟基构筑咔唑骨架的方法。该反应使用多个氢键合双官能硫脲作为催化剂，并且高度非对映体和对映体选择性（高达> 20：1 dr和> 99％ee）。制备规模的实验和产品的多功能转化证明了该方案。催化剂中的多个氢键在反应性和立体选择性中起关键作用。
• 2-Amino-1,4-dihydropyridine derivatives
  申请人：Bayer Aktiengesellschaft

  公开号：US03935223A1

  公开（公告）日：1976-01-27

  2-Amino-1,4-dihydropyridines bearing a carbonyl function in the 5-position and being optionally substituted by lower alkyl or phenyl in the 6-position, and the corresponding 2-amino-1,4,5,6,7,8-hexahydro-5-oxoquinolines, which derivatives are further substituted by a carbonyl group in the 3-position and optionally substituted in the 4-position by lower alkyl, phenyl, substituted phenyl or a heterocyclic group are anti-hypertensive agents and coronary vessel dilators. The compounds, of which 2-amino-6-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 3,5-diethyl ester is a representative embodiment, are prepared through condensation of an ylideneacetoacetic acid ester and an amidine.

  在5位带有羰基功能，6位可选择性地被低烷基或苯基取代的2-氨基-1,4-二氢吡啶和相应的2-氨基-1,4,5,6,7,8-六氢-5-氧代喹啉，其衍生物在3位进一步取代了羰基基团，4位可选择性地被低烷基、苯基、取代苯基或杂环基团取代，这些化合物是抗高血压药和冠状血管扩张剂。这些化合物通过酰乙酸乙酯和氨基嘧啶的缩合反应制备，其中2-氨基-6-甲基-4-(3-硝基苯基)-1,4-二氢吡啶-3,5-二羧酸二乙酯是代表性实施例。
• 2-Amino-4-pyrimidyl-1,4-dihydropyridine derivatives
  申请人：Bayer Aktiengesellschaft

  公开号：US04022898A1

  公开（公告）日：1977-05-10

  2-Amino-1,4-dihydropyridines bearing a carbonyl function in the 5-position and being optionally substituted by lower alkyl or phenyl in the 6-position, and the corresponding 2-amino-1,4,5,6,7,8-hexahydro-5-oxoquinolines, which derivatives are further substituted by a carbonyl group in the 3-position and optionally substituted in the 4-position by lower alkyl, phenyl, substituted phenyl or a heterocyclic group are antihypertensive agents and coronary vessel dilators. The compounds, of which 2-amino-6-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 3,5-diethyl ester is a representative embodiment, are prepared through condensation of an ylideneacetoacetic acid ester and an amidine.

  在5位带有羰基功能并在6位可选择取代为较低烷基或苯基的2-氨基-1,4-二氢吡啶和相应的2-氨基-1,4,5,6,7,8-六氢-5-氧喹啉衍生物，其衍生物在3位进一步取代为羰基基团并在4位可选择取代为较低烷基、苯基、取代苯基或杂环基团，可作为降压剂和冠状血管扩张剂。这些化合物通过酰乙酰乙酸酯和肼的缩合反应制备，其中2-氨基-6-甲基-4-(3-硝基苯基)-1,4-二氢吡啶-3,5-二羧酸3,5-二乙酯是一个代表性的实施例。