ethyl (E)-4-chloro-3-methylbut-2-enoate | 3621-52-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (E)-4-chloro-3-methylbut-2-enoate
• CAS: 3621-52-1
• 化学式: C₇H₁₁ClO₂
• 分子量: 162.616
• InChiKey: NJKFMYNBRXOKOL-GQCTYLIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  ethyl (E)-4-chloro-3-methylbut-2-enoate 在 N,N-二甲基丙烯基脲 、 正丁基锂 、 水 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 hexanes 、 二甲基亚砜 为溶剂， 反应 5.17h， 生成 阿维A酸
  参考文献：
  名称：

  Syntheses, antiproliferative activity and theoretical characterization of acitretin-type retinoids with changes in the lipophilic part

  摘要：

  Acitretin analogs, incorporating changes in the lipophilic part, were efficiently synthesized from commercially available aromatic aldehydes or methyl ketones using the Wittig or Horner-Wadsworth-Emmons reaction. Their antiproliferative activity was evaluated against human breast MCF-7 epithelial cells. Analogs 3, 4, 8 and 11 exhibited strong, dose-dependent, antiproliferative activity on the tested cell line. Analog 3, incorporating three methoxy groups in the aromatic ring, exhibited the strongest inhibitory effect at 10 mu M. High-level all electron conventional ab initio and density functional theory quantum chemical calculations were performed to obtain the molecular structure, electron charge distribution and polarization properties of all compounds of interest in this work. The most active analogs were planar and were characterized by larger dipole moments than the other synthesized molecules. Another factor of importance to the analysis of the activity of these molecules is the dipole polarizability. (C) 2010 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2010.12.008
• 作为产物：
  描述：

  ethyl (E)-4-hydroxy-3-methyl-2-butenoate 在 四氯化碳 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以63%的产率得到ethyl (E)-4-chloro-3-methylbut-2-enoate
  参考文献：
  名称：

  Syntheses, antiproliferative activity and theoretical characterization of acitretin-type retinoids with changes in the lipophilic part

  摘要：

  Acitretin analogs, incorporating changes in the lipophilic part, were efficiently synthesized from commercially available aromatic aldehydes or methyl ketones using the Wittig or Horner-Wadsworth-Emmons reaction. Their antiproliferative activity was evaluated against human breast MCF-7 epithelial cells. Analogs 3, 4, 8 and 11 exhibited strong, dose-dependent, antiproliferative activity on the tested cell line. Analog 3, incorporating three methoxy groups in the aromatic ring, exhibited the strongest inhibitory effect at 10 mu M. High-level all electron conventional ab initio and density functional theory quantum chemical calculations were performed to obtain the molecular structure, electron charge distribution and polarization properties of all compounds of interest in this work. The most active analogs were planar and were characterized by larger dipole moments than the other synthesized molecules. Another factor of importance to the analysis of the activity of these molecules is the dipole polarizability. (C) 2010 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2010.12.008

文献信息

• Efficient syntheses of climate relevant isoprene nitrates and (1<i>R</i>,5<i>S</i>)-(−)-myrtenol nitrate
  作者：Sean P Bew、Glyn D Hiatt-Gipson、Graham P Mills、Claire E Reeves

  DOI：10.3762/bjoc.12.103

  日期：——

  chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-met

  在这里，我们报告了几种重要的，与气候相关的硝酸异戊二烯的化学选择性合成，这些合成的硝酸异戊二烯使用硝酸银来介导“卤化物取代硝酸盐”。利用易于获得的起始原料，试剂和霍纳-沃兹沃思-埃蒙斯化学方法合成易于分离的，合成通用的“关键构件”（E）-和（Z）-3-甲基-4-氯丁-2-en-1-使用便宜的“现货”材料已经获得了醇以及（E）-和（Z）-1-（（（2-甲基-4-溴丁-2-烯氧基）甲基）-4-甲氧基苯。利用它们的反应性，我们研究了它们进行“硝酸烯丙基卤代烯丙基卤”取代反应的能力，我们证明了生成（E）-和（Z）-3-甲基-4-羟基丁-2-烯基硝酸酯，以及（E） -和（Z）-2-甲基-4-羟基丁-2-烯基硝酸盐（'异戊二烯硝酸盐' ），总产率为66-80％。使用NOESY实验，已经建立了纯化的异戊二烯硝酸盐中的碳-碳双键构型的阐明。进一步举例说明我们的“硝酸盐卤化物”取代化学，我们概述了（1R，2
• Asymmetric Reductive Carbocyclization Using Engineered Ene Reductases
  作者：Kathrin Heckenbichler、Anna Schweiger、Lea Alexandra Brandner、Alexandra Binter、Marina Toplak、Peter Macheroux、Karl Gruber、Rolf Breinbauer

  DOI：10.1002/anie.201802962

  日期：2018.6.11

  bearing an electron‐withdrawing group, for example, a carbonyl group. This asymmetric reduction has been exploited for biocatalysis. Going beyond its canonical function, we show that members of this enzyme family can also catalyze the formation of C−C bonds. α,β‐Unsaturated aldehydes and ketones containing an additional electrophilic group undergo reductive cyclization. Mechanistically, the two‐electron‐reduced

  来自老黄酶 (OYE) 家族的烯还原酶可还原带有吸电子基团（例如羰基）的 α,β-不饱和化合物中的 C=C 双键。这种不对称还原已被用于生物催化。除了其典型功能之外，我们还发现该酶家族的成员还可以催化 C−C 键的形成。含有额外亲电基团的 α,β-不饱和醛和酮会发生还原环化。从机制上讲，双电子还原酶辅因子 FMN 传递氢化物以生成烯醇化物中间体，该中间体与内部亲电子试剂发生反应。用非质子 Phe 或 Trp 单位点取代关键的 Tyr 残基有利于环化反应而不是自然还原反应。新的转化使得对映选择性合成手性环丙烷的效率高达 >99% 。
• Late‐Stage Chemoenzymatic Installation of Hydroxy‐Bearing Allyl Moiety on the Indole Ring of Tryptophan‐Containing Peptides
  作者：Nagaraju Mupparapu、Lauren Brewster、Katrina F. Ostrom、Sherif I. Elshahawi

  DOI：10.1002/chem.202104614

  日期：2022.4.6

  The late-stage functionalization of indole- and tryptophan (Trp)-containing compounds with reactive moieties facilitates downstream diversification and leads to changes in their biological properties. The synthesis of two hydroxy-bearing allyl pyrophosphates is described and a chemoenzymatic method is demonstrated which uses a promiscuous indole prenyltransferase (IPT) enzyme to install a dual reactive

  具有反应性部分的含吲哚和色氨酸 (Trp) 化合物的后期功能化促进了下游的多样化并导致其生物学特性的变化。描述了两种带有羟基的烯丙基焦磷酸酯的合成，并证明了一种化学酶法，该方法使用混杂的吲哚异戊二烯基转移酶 (IPT) 酶将双反应性的带有羟基的烯丙基直接安装在含色氨酸肽的吲哚环上。
• Total synthesis of (−)-kainic acid and (+)-allo-kainic acid through SmI₂-mediated intramolecular coupling between allyl chloride and an α,β-unsaturated ester
  作者：Junya Suzuki、Natsumi Miyano、Shunpei Yashiro、Taiki Umezawa、Fuyuhiko Matsuda

  DOI：10.1039/c7ob01427a

  日期：——

  cyclized through SmI2-mediated reductive coupling between allyl chloride and an α,β-unsaturated ester, although little has been reported about SmI2-promoted C–C bond formation of an allyl chloride with an α,β-unsaturated ester. Selection of either the 3,4-cis- or 3,4-trans-selective cyclization can be accomplished simply by changing the additives from NiI2 to HMPA during reductive cyclization conducted in

  通过SmI 2介导的烯丙基氯与α，β-不饱和酯之间的还原偶联，可将3,4-二取代的吡咯烷环有效地环化，尽管关于SmI 2促进烯丙基氯与C，C形成C-C键的报道很少。 α，β-不饱和酯。通过在H 2 O-THF中进行还原环化过程中，将添加剂从NiI 2改为HMPA，可以简单地选择3,4-顺式或3,4-反式选择性环化。（-）-海藻酸和（+）-别铝的全合成-海藻酸，是在神经科学和神经药理学中用作有用分子探针的吡咯烷生物碱，是通过使用SmI 2促进的立体互补闭环反应来构建2,3,4-三取代吡咯烷骨架的类胡萝卜素而成功实现的。
• Syntheses, antiproliferative activity and theoretical characterization of acitretin-type retinoids with changes in the lipophilic part
  作者：George E. Magoulas、Stavros E. Bariamis、Constantinos M. Athanassopoulos、Anastasios Haskopoulos、Petros G. Dedes、Marios G. Krokidis、Nikos K. Karamanos、Dimitris Kletsas、Dionissios Papaioannou、George Maroulis

  DOI：10.1016/j.ejmech.2010.12.008

  日期：2011.2

  Acitretin analogs, incorporating changes in the lipophilic part, were efficiently synthesized from commercially available aromatic aldehydes or methyl ketones using the Wittig or Horner-Wadsworth-Emmons reaction. Their antiproliferative activity was evaluated against human breast MCF-7 epithelial cells. Analogs 3, 4, 8 and 11 exhibited strong, dose-dependent, antiproliferative activity on the tested cell line. Analog 3, incorporating three methoxy groups in the aromatic ring, exhibited the strongest inhibitory effect at 10 mu M. High-level all electron conventional ab initio and density functional theory quantum chemical calculations were performed to obtain the molecular structure, electron charge distribution and polarization properties of all compounds of interest in this work. The most active analogs were planar and were characterized by larger dipole moments than the other synthesized molecules. Another factor of importance to the analysis of the activity of these molecules is the dipole polarizability. (C) 2010 Elsevier Masson SAS. All rights reserved.