Methyl (E/Z)-5-(2-methyl-1,3-dioxocyclopent-2-yl)-2-pentenoate | 66977-01-3

• 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: Methyl (E/Z)-5-(2-methyl-1,3-dioxocyclopent-2-yl)-2-pentenoate
• 英文别名: methyl 5-(1-methyl-2,5-dioxocyclopentyl)pent-2-enoate
• CAS: 66977-01-3
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: YKLWTPZFHBDQIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.43
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  60.44
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Methyl (E/Z)-5-(2-methyl-1,3-dioxocyclopent-2-yl)-2-pentenoate 在 1% Pd/C 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 5.0h， 以100%的产率得到5-(1-Methyl-2,5-dioxo-cyclopentyl)-pentanoic acid methyl ester
  参考文献：
  名称：

  由2-甲基-1,3-环烷二酮和2-甲基环烷酮衍生的外消旋和对映体纯的乙酰基ω-酮酯的合成

  摘要：

  从常见的中间体开始容易地获得分别连接到2-甲基-1,3-环烷二酮和2-甲基环烷酮的外消旋和对映体纯的炔基酯，这些中间体可以大规模获得。 炔基酯-对映体链-伸长率-三甲基甲硅烷基丙炔-Corey-Fuchs反应

  DOI：

  10.1055/s-0029-1217043
• 作为产物：
  描述：

  3-(1-methyl-2,5-dioxocyclopentyl)propanal 、 甲氧羰基亚甲基三苯基正膦 以 二氯甲烷 为溶剂， 反应 4.0h， 以95%的产率得到Methyl (E/Z)-5-(2-methyl-1,3-dioxocyclopent-2-yl)-2-pentenoate
  参考文献：
  名称：

  由2-甲基-1,3-环烷二酮和2-甲基环烷酮衍生的外消旋和对映体纯的乙酰基ω-酮酯的合成

  摘要：

  从常见的中间体开始容易地获得分别连接到2-甲基-1,3-环烷二酮和2-甲基环烷酮的外消旋和对映体纯的炔基酯，这些中间体可以大规模获得。 炔基酯-对映体链-伸长率-三甲基甲硅烷基丙炔-Corey-Fuchs反应

  DOI：

  10.1055/s-0029-1217043

文献信息

• Phosphine-Catalyzed Reactions of Activated Olefins Tethered to Cycloalkanones. Substrate- and Solvent-Controlled Synthesis of Bicyclo[3.2.1]octanones, Mixed Acetals, and Morita–Baylis–Hillman Products
  作者：Yanhui Wang、Alexis Jaunet、Philippe Geoffroy、Michel Miesch

  DOI：10.1021/ol403039b

  日期：2013.12.20

  organocatalyzed reaction of cycloalkanones, i.e., cyclopentanones or 1,3-cyclopentanediones tethered to actived olefins, afforded selectively and in high yields three different types of products: bicyclo[3.2.1]octanones, mixed acetals, and Morita–Baylis–Hillman products. The progress of the reaction was closely related to the reaction medium and to the length of the tether located between the cyclopentanone (-dione)

  所述Ñ -Bu 3 P organocatalyzed环烷酮的反应，即，环戊酮或1,3- cyclopentanediones拴actived烯烃，选择性地提供并以高收率三种不同类型的产品：双环[3.2.1] octanones，混合缩醛和森田–Baylis–Hillman产品。反应的进展与反应介质以及位于环戊酮（-二酮）和活化的烯烃之间的系链的长度密切相关。
• 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.
• Synthesis of Racemic and Enantiomerically Pure Acetylenic ω-Keto Esters Derived from 2-Methyl-1,3-cycloalkanediones and 2-Methylcycloalkanones Respectively
  作者：Michel Miesch、Philippe Geoffroy、Marie-Paule Ballet、Sidonie Finck、Eric Marchioni、Christophe Marcic

  DOI：10.1055/s-0029-1217043

  日期：2010.1

  Racemic and enantiomerically pure alkynyl esters tethered, respectively, to 2-methyl-1,3-cycloalkanediones and 2-methyl­cycloalkanones were readily obtained starting from common intermediates, which were available on large scale. alkynyl ester - enantiomer-chain - elongation - trimethylsilylpropyne - Corey-Fuchs reaction

  从常见的中间体开始容易地获得分别连接到2-甲基-1,3-环烷二酮和2-甲基环烷酮的外消旋和对映体纯的炔基酯，这些中间体可以大规模获得。 炔基酯-对映体链-伸长率-三甲基甲硅烷基丙炔-Corey-Fuchs反应