methyl 2-(4-chlorophenyl)carbonylprop-2-enoate

• 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 2-(4-chlorophenyl)carbonylprop-2-enoate
• 英文别名: methyl 2-(4-chlorobenzoyl)acrylate；Methyl 2-(4-chlorobenzoyl)prop-2-enoate；methyl 2-(4-chlorobenzoyl)prop-2-enoate
• 化学式: C₁₁H₉ClO₃
• 分子量: 224.644
• InChiKey: BCRXTRXVVBIGOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-(4-chlorophenyl)carbonylprop-2-enoate 在 Rhodotorula glutinis CCT 2182 yeast 作用下， 以 乙醇 、 水 为溶剂， 反应 84.0h， 以21%的产率得到methyl 3-(4-chlorophenyl)-2-methyl-3-oxopropanoate
  参考文献：
  名称：

  Regio- and enantioselective bioreduction of methyleneketoesters using both polymeric resin and cellulose matrix

  摘要：

  Methyleneketoesters were prepared in >90% yield by performing an IBX oxidation of Morita-Baylis-Hillman adducts. A methodology was developed to achieve methyl 3-aryl-3-keto-2-methylenepropanoate reduction using a screening of yeast strains in three different reaction procedures to obtain products with both high yield and diastereoselectivity. The reactions conducted in water provided inferior yields (50%) for substrates 2b-c. Employing Amberlite (R) XAD7HP which was a substrate reservoir that also immediately extracted the products from the reaction medium after their formation, syn-4a-c and anti-4a-c were isolated in 60-70% yield, with high stereoselectivity (98-99% ee). The best results were obtained using substrates adsorbed on filter paper which provided products yields above 70%, a 99% ee and a diastereomoeric ratio (syn-4: anti-4) 9:1. Cellulose matrix has excellent potential to be successfully employed in general biocatalytic reactions. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2013.09.018
• 作为产物：
  描述：

  2-[(4-氯苯基)-羟基甲基]-丙烯酸甲酯 在 2-碘酰基苯甲酸 作用下， 以 乙腈 为溶剂， 生成 methyl 2-(4-chlorophenyl)carbonylprop-2-enoate
  参考文献：
  名称：

  通过意外的碳-碳键裂解将肼插入N'-烷基苯甲酰肼的路线。

  摘要：

  衍生自Morita-Baylis-Hillman加合物的丙烯酸苯甲酰酯与肼反应中的偶然碳-碳键裂解，生成了新的N'，N'-二取代苯并酰肼。该反应的特征在于两个碳-氮键的区域选择性形成，并且与一系列丙烯酸酯和肼反应良好。简短的机械研究暗示周期性半胱氨酸可能是中间产物。

  DOI：

  10.1021/acs.orglett.9b02657

文献信息

• Hypervalent iodine catalysis for selective oxidation of Baylis–Hillman adducts via in situ generation of o-iodoxybenzoic acid (IBX) from 2-iodosobenzoic acid (IBA) in the presence of oxone
  作者：Raktani Bikshapathi、Parvathaneni Sai Prathima、Vaidya Jayathirtha Rao

  DOI：10.1039/c6nj02628a

  日期：——

  An efficient, environmentally benign, eco-friendly protocol for selective oxidation of primary and secondary Baylis–Hillman alcohols to the corresponding carbonyl compounds has been developed. We have demonstrated the catalytic use of o-iodoxybenzoic acid (IBX) generated in situ from 2-iodosobenzoic acid (IBA) in the presence of oxone (2KHSO5·KHSO4·K2SO4) as a co-oxidant. This efficient method notably

  已经开发出一种有效的，对环境无害的，环境友好的方案，用于将伯利兹和仲伯利兹-希尔曼醇选择性氧化为相应的羰基化合物。我们已经证明了在氧酮（2KHSO 5 ·KHSO 4 ·K 2 SO 4）作为助氧化剂存在下，由2-碘代苯甲酸（IBA）原位生成的邻碘氧苯甲酸（IBX）的催化用途。这种有效的方法尤其可以在不使用任何有毒重金属和直接使用棘手的IBX的情况下更好地提高产量。此外，可以通过还原后处理方便地回收合成的催化剂。
• [3 + 2] Annulations between indoles and α,β-unsaturated ketones: access to pyrrolo[1,2-a]indoles and model reactions toward the originally assigned structure of yuremamine
  作者：Haokun Li、Zhonglei Wang、Liansuo Zu

  DOI：10.1039/c5ra11904a

  日期：——

  A direct [3 + 2] annulation reaction between indoles and α,β-unsaturated ketones is reported, which allows for the efficient assembly of densely substituted, highly functionalized pyrrolo[1,2-a]indoles. Model reactions toward the originally assigned structure of yuremamine are also described, leading to the successful construction of the core with required functionality.

  据报道吲哚和α，β-不饱和酮之间有直接的[3 + 2]环化反应，可以有效地组装密集取代的高度官能化的吡咯并[1,2- a ]吲哚。还描述了针对最初分配的紫杉胺结构的模型反应，从而成功构建了具有所需功能的核。
• Stereoselective Radical Cyclization Cascades Triggered by Addition of Diverse Radicals to Alkynes To Construct 6(5)–6–5 Fused Rings
  作者：Lin Huang、Liu Ye、Xiao-Hua Li、Zhong-Liang Li、Jin-Shun Lin、Xin-Yuan Liu

  DOI：10.1021/acs.orglett.6b02599

  日期：2016.10.21

  Cascade radical cyclization of alkynyl ketones with various carbon- and heteroatom-centered radical precursors via a sequential radical addition/1,5-H radical shift/5-exo-trig/radical cyclization process was realized for the first time. This method provides a strategically novel and step-economical protocol for diversity-oriented synthesis of a wide range of carbocyclic and heterocyclic 6(5)–6–5 fused

  首次实现了通过连续的自由基加成/ 1,5-H自由基转移/ 5 -exo-trig /自由基环化过程，将具有各种以碳原子和杂原子为中心的自由基前体进行的炔基酮的级联自由基环化。该方法为广泛的具有三个连续立体中心的碳环和杂环6（5）–6–5稠合环系统的多样性导向合成提供了战略上新颖且经济的步骤，其中包括高产率的季碳和出色的化学-和非对映选择性。
• A Hydrazine Insertion Route to <i>N</i>′-Alkyl Benzohydrazides by an Unexpected Carbon–Carbon Bond Cleavage
  作者：Ajit Kumar Jha、Rajkiran Kumari、Srinivasan Easwar

  DOI：10.1021/acs.orglett.9b02657

  日期：2019.10.18

  A serendipitous carbon-carbon bond cleavage in the reaction of benzoyl acrylates, derived from Morita-Baylis-Hillman adducts, with hydrazines delivered new N',N'-disubstituted benzohydrazides. The reaction features a regioselective formation of two carbon-nitrogen bonds and works well with a range of acrylates and hydrazines. A brief mechanistic investigation alluded to a cyclic hemiaminal as a plausible

  衍生自Morita-Baylis-Hillman加合物的丙烯酸苯甲酰酯与肼反应中的偶然碳-碳键裂解，生成了新的N'，N'-二取代苯并酰肼。该反应的特征在于两个碳-氮键的区域选择性形成，并且与一系列丙烯酸酯和肼反应良好。简短的机械研究暗示周期性半胱氨酸可能是中间产物。
• Diamine-mediated degradative dimerisation of Morita–Baylis–Hillman ketones
  作者：Ajit Kumar Jha、Anju Kumari、Srinivasan Easwar

  DOI：10.1039/c9cc10068g

  日期：——

  A degradative dimerisation of Morita-Baylis-Hillman ketones was observed in the presence of a primary diamine. The reaction proceeded swiftly to produce methylene-bridged 1,3-dicarbonyl compounds. A brief mechanistic investigation alluded to a retro-Mannich reaction as the key step of the transformation.

  在伯二胺存在下，观察到森田-贝利斯-希尔曼酮的降解性二聚化。反应迅速进行以产生亚甲基桥连的1，3-二羰基化合物。简短的机械研究暗示了曼尼奇的后反应是这一转变的关键步骤。