(E)-2-(methoxycarbonylmethylene)-5-methyltetrahydrofuran | 246137-39-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢呋喃
• 英文名称: (E)-2-(methoxycarbonylmethylene)-5-methyltetrahydrofuran
• 英文别名: 2E-[(methoxycarbonyl)methylene]-5-methyltetrahydrofuran；methyl (5-methyldihydrofuran-2(3H)-ylidene)acetate；methyl (2E)-2-(5-methyloxolan-2-ylidene)acetate
• CAS: 246137-39-3
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: OSKPHNFOIQIJSF-FNORWQNLSA-N

物化性质

• 沸点：
  215.4±19.0 °C(Predicted)
• 密度：
  1.140±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-2-(methoxycarbonylmethylene)-5-methyltetrahydrofuran 在 三溴化硼 、 水 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到6-bromo-3-oxoheptanoic acid methyl ester
  参考文献：
  名称：

  2-亚烷基四氢呋喃与三溴化硼的反应：应用“环化-开环”策略化学和区域选择性合成 6-Bromo-3-oxoalkanoates

  摘要：

  Bromo-3-oxoalkanoates、benzofurans 和 1,7-dibro-heptan-4-ones 是通过 2-亚烷基四氢呋喃与三溴化硼反应的化学和区域选择性制备的。

  DOI：

  10.1055/s-2004-830893
• 作为产物：
  描述：

  2,2-Dimethyl-6-(3-tert-butyldimethylsilyloxybutyl)-1,3-dioxin-4-one 在 溶剂黄146 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 2.0h， 生成 (E)-2-(methoxycarbonylmethylene)-5-methyltetrahydrofuran
  参考文献：
  名称：

  Two lactone formation reactions from 1,3-dioxin-4-ones having hydroxyalkyl group at the 6-position: Difference in ring opening and closure

  摘要：

  Two methods (A: ring opening to acylketenes followed by intramolecular ketene trapping and B: methoxide-mediated ring opening followed by cyclization of the hydroxy esters thus formed) have become available for the synthesis of lactones and/or cyclic ethers from 1,3-dioxin-4-ones having 1-approximately 4-hydroxyalkyl group at the 6-position. Mechanism and scope of both methods have been clarified.

  DOI：

  10.1016/s0040-4020(01)86522-4

文献信息

• New carbon carbon bond forming reactions of cyclic sulfate esters and cyclic sulfamidates
  作者：Melanie K Pound、Darren L Davies、Melanie Pilkington、Maria M de Pina Vaz Sousa、John D Wallis

  DOI：10.1016/s0040-4039(02)00138-7

  日期：2002.3

  Carbon–carbon bonding forming reactions of two cyclic sulfate esters and a cyclic sulfamidate are reported, the former with lithium dianions to give substituted tetrahydrofuran derivatives with displacement of sulfate, and the latter undergoes ring-opening monosubstitution reactions with stabilised organolithiums and an organocuprate species.

  据报道，有两种环状硫酸酯和环状氨基磺酸盐的碳-碳键形成反应，前者与锂二价阴离子可取代硫酸根而得到取代的四氢呋喃衍生物，后者则与稳定的有机锂和有机铜酸盐发生开环单取代反应。
• Reaction of thionolactones with zinc enolate: new synthesis of vinylogous carbonates
  作者：Hyeon Kyu Lee、Jia Kim、Chwang Siek Pak

  DOI：10.1016/s0040-4039(99)01231-9

  日期：1999.8

  Reaction of various thionolactones, prepared from the lactones and Lawesson's reagent, with methyl bromozinc-acetate afforded the corresponding vinylogous carbonates in good yields under mild conditions. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Enantioselective synthesis of 2-alkylidenetetrahydrofurans based on a ‘cyclization/enzymatic resolution’ strategy
  作者：Esen Bellur、Dominique Böttcher、Uwe Bornscheuer、Peter Langer

  DOI：10.1016/j.tetasy.2006.03.006

  日期：2006.3

  Enantionterically pure 2-alkylidenetetrahydrofurans have been prepared by TiCl4 mediated enantiospecific reactions of 1,3-bis-silyl enol ethers with enantiomerically pure epichlorohydrin. In addition, the enzymatic kinetic resolution of 2-alkylidenetetrahydrofurans, using Candida antarctica lipase B (CAL-B), was studied. Enzymatic kinetic resolution of monocyclic 5-vinyl-2-alkylidenetetrahydrofuran with CAL-B afforded the enantiomerically pure ester with 97% ee. For a bicyclic 2-alkylidenetetrahydrofuran, this proceeded with excellent enantioselectivity (E > 100) affording the enantiomerically pure acid with 98% ee. 2-Alkylidenetetrahydrofurans were prepared by [3+2] cyclization reactions of 1,3-dicarbonyl dianions ('free dianions') or 1,3-bis-silyl enol ethers ('masked dianions'). (c) 2006 Published by Elsevier Ltd.
• Palladium-catalyzed synthesis of 2E-[(methoxycarbonyl)methylene]tetrahydrofurans: oxidative cyclization–methoxycarbonylation of 4-yn-1-ols versus cycloisomerization–hydromethoxylation
  作者：Bartolo Gabriele、Giuseppe Salerno、Francesca De Pascali、Mirco Costa、Gian Paolo Chiusoli

  DOI：10.1016/s0022-328x(99)00492-1

  日期：2000.1

  4-Yn-1-ols bearing a terminal triple bond undergo oxidative cyclization-alkoxycarbonylation in methanol at 70 degrees C and 100 atm of a 9:1 mixture of carbon monoxide and air in the presence of catalytic amounts of [PdI4](2-) in conjunction with an excess of KI to give 2E-[(methoxycarbonyl)methylene]tetrahydrofurans in good yields. A competing reaction, cycloisomerization-hydromethoxylation leading to 2-methoxy-2-methyltetrahydrofurans, can be easily curtailed by increasing the KI excess. The latter products can be prepared from 4-yn-1-ols and methanol in high yields using the same catalytic system and without KI excess in the absence of carbon monoxide. (C) 2000 Elsevier Science S.A. All rights reserved.
• Two lactone formation reactions from 1,3-dioxin-4-ones having hydroxyalkyl group at the 6-position: Difference in ring opening and closure
  作者：Masayuki Sato、Jun-ichi Sakaki、Yoshiaki Sugita、Sanae Yasuda、Hiroko Sakoda、Chikara Kaneko

  DOI：10.1016/s0040-4020(01)86522-4

  日期：1991.7

  Two methods (A: ring opening to acylketenes followed by intramolecular ketene trapping and B: methoxide-mediated ring opening followed by cyclization of the hydroxy esters thus formed) have become available for the synthesis of lactones and/or cyclic ethers from 1,3-dioxin-4-ones having 1-approximately 4-hydroxyalkyl group at the 6-position. Mechanism and scope of both methods have been clarified.