Methyl (E)-4--2-butenoate

• 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 (E)-4--2-butenoate
• 英文别名: methyl (E)-4-(N-(2-oxopropyl)-4-methylphenylsulfonamido)but-2-enoate；methyl (E)-4-[(4-methylphenyl)sulfonyl-(2-oxopropyl)amino]but-2-enoate
• 化学式: C₁₅H₁₉NO₅S
• 分子量: 325.386
• InChiKey: FXIKKNJZJVKBPW-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  89.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  丙酮氰醇 、 Methyl (E)-4--2-butenoate 在 四丁基溴化铵 、 caesium carbonate 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以90%的产率得到methyl (2R*,6S*)-2-(6-cyano-6-methyl-4-tosylmorpholin-2-yl)acetate
  参考文献：
  名称：

  通过相转移催化化学杂合制备各种杂环化合物：功能化哌啶的对映选择性合成

  摘要：

  在这项工作中，提出了一种基于相转移催化（PTC）制备各种饱和杂环的新的化学发散性多米诺骨牌方法。双亲电子底物的多用途性质（同时显示迈克尔受体和酮）被杂原子束缚，实现了三种不同的多米诺反应途径。亲核试剂决定了反应的化学选择性。磺基-迈克尔/羟醛，氰化物加成/氧-迈克尔和迈克尔/ H-移位/羟醛过程，以及束缚杂原子的变化，导致形成六种不同类别的饱和杂环。DFT计算考虑了两个生产率最高的过程中观察到的化学选择性和非对映选择性。此外，对磺胺-迈克尔/醛醇通道进行了广泛的研究，

  DOI：

  10.1002/adsc.201901500
• 作为产物：
  描述：

  4-溴-2-丁烯酸甲酯 在 potassium carbonate 、 三氟乙酸 、 sodium iodide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 15.0h， 生成 Methyl (E)-4--2-butenoate
  参考文献：
  名称：

  Access to Polyfunctionalized Chiral Piperidines through Enantioselective Addition–Carbocyclization Cascade Reaction Catalyzed by a Rhodium(I)–Diene Complex

  摘要：

  A new addition-carbocyclization cascade reaction initiated by arylboronic acids and catalyzed by a rhodium/chiral diene complex is described. Starting from N-bridged oxoenoate derivatives, highly functionalized piperidines bearing three contiguous stereogenic centers were obtained with excellent enantio- and diastereoselectivities.

  DOI：

  10.1021/acs.orglett.5b02858

文献信息

• Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol
  作者：Ge Hyeong Lee、Eun Bok Choi、Eun Lee、Chwang Siek Pak

  DOI：10.1021/jo00085a036

  日期：1994.3

  The reductive cyclizations of various ketones tethered to activated olefins such as alpha,beta-unsaturated esters, nitriles, sulfoxides, and sulfides were mediated by magnesium in dry methanol in the presence of mercuric chloride. When treated with magnesium in dry methanol at -23-degrees-C all of the ketones except nitrile 9 (42%) and 5-oxa-8-keto-2-enoate 5 (13%) gave excellent yields (79-98%) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the beta-carbon of the activated olefin and the carbonyl carbon. The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst. For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups. The product isomer ratios were independent of the substrate geometry (E or Z). In contrast to the ketones, aldehydes tethered to alpha,beta-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products. When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved. Under the same reaction conditions alpha,beta-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85%) as the major product along with a small amount (9%) of cyclized product 19t. In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54%). With excess magnesium (15 equiv), however, alpha,beta-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95%) via deoxygenated sulfide 18. Both 16Z and 16E afforded product 19t as a single isomer. It is suggested that the reductive cyclization of the alpha,beta-unsaturated esters and nitriles proceed by means of nucleophilic attack of a beta-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group. The cyclization of the alpha,beta-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.
• Chemodivergent Preparation of Various Heterocycles <i>via</i> Phase‐Transfer Catalysis: Enantioselective Synthesis of Functionalized Piperidines
  作者：Giulio Bertuzzi、Filippo Silvestrini、Pierluigi Moimare、Daniel Pecorari、Andrea Mazzanti、Luca Bernardi、Mariafrancesca Fochi

  DOI：10.1002/adsc.201901500

  日期：2020.3.4

  In this work, a new chemodivergent domino approach for the preparation of various saturated heterocycles, based on phase‐transfer catalysis (PTC), is presented. The versatile nature of doubly electrophilic substrates, showing both a Michael acceptor and a ketone, tethered by a heteroatom, enables three different domino reaction pathways. The nucleophile dictates the chemoselectivity of the reaction

  在这项工作中，提出了一种基于相转移催化（PTC）制备各种饱和杂环的新的化学发散性多米诺骨牌方法。双亲电子底物的多用途性质（同时显示迈克尔受体和酮）被杂原子束缚，实现了三种不同的多米诺反应途径。亲核试剂决定了反应的化学选择性。磺基-迈克尔/羟醛，氰化物加成/氧-迈克尔和迈克尔/ H-移位/羟醛过程，以及束缚杂原子的变化，导致形成六种不同类别的饱和杂环。DFT计算考虑了两个生产率最高的过程中观察到的化学选择性和非对映选择性。此外，对磺胺-迈克尔/醛醇通道进行了广泛的研究，
• Access to Polyfunctionalized Chiral Piperidines through Enantioselective Addition–Carbocyclization Cascade Reaction Catalyzed by a Rhodium(I)–Diene Complex
  作者：Fabien Serpier、Jean-Louis Brayer、Benoît Folléas、Sylvain Darses

  DOI：10.1021/acs.orglett.5b02858

  日期：2015.11.6

  A new addition-carbocyclization cascade reaction initiated by arylboronic acids and catalyzed by a rhodium/chiral diene complex is described. Starting from N-bridged oxoenoate derivatives, highly functionalized piperidines bearing three contiguous stereogenic centers were obtained with excellent enantio- and diastereoselectivities.