allyl 2-allyl-3-oxobutanoate | 123326-16-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: allyl 2-allyl-3-oxobutanoate
• 英文别名: 2-Allyl-3-oxo-buttersaeure-allyl-ester；Prop-2-enyl 2-acetylpent-4-enoate
• CAS: 123326-16-9
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: HSOONMNVUKOHJZ-UHFFFAOYSA-N

物化性质

• 沸点：
  113 °C(Press: 20 Torr)
• 密度：
  0.986±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  allyl 2-allyl-3-oxobutanoate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 trans-(E,E)-4,11-diacetyl-5,12-dioxo-6,13-dioxa-1,8-cyclotetradecadiene
  参考文献：
  名称：

  α-乙酰内酯的合成；通过尝试直接环闭合获得 14 元双内酯

  摘要：

  α-乙酰内酯可通过向山-克莱森反应获得。通过 4-碘丁基乙酰乙酸酯的分子内烷基化或 2-烯丙基-3-氧代丁酸烯丙酯的烯烃复分解，尝试直接 7 元环闭合，仅提供二聚体 14 元环产物而不是预期的己内酯。

  DOI：

  10.1055/s-2002-31907
• 作为产物：
  描述：

  3-Allyloxy-but-2c-ensaeure-allylester 在 (thermolysis) 作用下， 生成 allyl 2-allyl-3-oxobutanoate
  参考文献：
  名称：

  Preparation and Thermal Rearrangement of Alkenyl 3-Alkenyloxy-2-butenoates. Catalysis of the Aliphatic Claisen Rearrangement by Ammonium Chloride

  摘要：

  DOI：

  10.1021/jo01047a061

文献信息

• Synthesis and metathesis reactions of a phosphine-free dihydroimidazole carbene ruthenium complex
  作者：Simon Gessler、Stefan Randl、Siegfried Blechert

  DOI：10.1016/s0040-4039(00)01808-6

  日期：2000.12

  Synthesis and activity in ring closure metathesis (RCM) and cross metathesis (CM) of the phosphine-free 1,3-dimesityl-4,5-dihydroimidazole-2-ylidene (IHMes) ruthenium alkoxybenzylidene complex 6 are reported.

  报道了无膦的1,3-二甲硅烷基-1,4,5-二氢咪唑-2-亚烷基（IHMes）钌烷氧基亚苄基配合物6的合成及其在闭环复分解（RCM）和交叉复分解（CM）中的活性。
• Stereochemical Control in Microbial Reduction. 9. Diastereoselective Reduction of 2-Alkyl-3-oxobutanoate with Bakers’ Yeast
  作者：Kaoru Nakamura、Takehiko Miyai、Ashish Nagar、Shinzaburo Oka、Atsuyoshi Ohno

  DOI：10.1246/bcsj.62.1179

  日期：1989.4.15

  Bakers’ yeast reduces esters of 2-alkyl-3-oxobutanoic acid (CH3COCHRCO2R′; R=methyl, ethyl, propyl, propargyl, and allyl) into the corresponding (S)-hydroxy esters with exclusive stereoselectivity, while the configuration at the 2-position of the hydroxy esters is either S (anti) or R (syn) depending on the structure of the alkoxyl group in the carboalkoxyl moiety of the ester. Oftenly, the stereoselectivity

  面包师的酵母将 2-烷基-3-氧代丁酸（CH3COCHRCO2R'；R=甲基、乙基、丙基、炔丙基和烯丙基）的酯还原为相应的（S）-羟基酯，具有独特的立体选择性，而在 2羟基酯的-位是S(反)或R(syn)，这取决于酯的碳烷氧基部分中烷氧基的结构。通常，关于 2 位的立体选择性并不令人满意。一般来说，叔丁酯的还原在产物中占主导地位，而 1,1-二甲基丙酯的还原则发挥顺式优势。从酯的合理构象的角度讨论了这两种酯在非对映选择性方面的显着差异。
• Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides
  作者：Ivan A. Yaremenko、Yulia Yu. Belyakova、Peter S. Radulov、Roman A. Novikov、Michael G. Medvedev、Nikolai V. Krivoshchapov、Alexander A. Korlyukov、Igor V. Alabugin、Alexander O. Terent’ev

  DOI：10.1021/jacs.1c02249

  日期：2021.5.5

  Stable bridged azaozonides can be selectively assembled via a catalyst-free three-component condensation of 1,5-diketones, hydrogen peroxide, and an NH-group source such as aqueous ammonia or ammonium salts. This procedure is scalable and can produce gram quantities of bicyclic stereochemically rich heterocycles. The new azaozonides are thermally stable and can be stored at room temperature for several

  通过 1,5-二酮、过氧化氢和氨水或铵盐等 NH 基团源的无催化剂三组分缩合反应，可以选择性地组装稳定的桥连氮杂化合物。该程序是可扩展的，可以产生克数量的双环立体化学丰富的杂环。新的氮杂化合物具有热稳定性，可在室温下储存数月而不分解，在 -10 °C 下可储存至少 1 年。对偶氮化合物的化学稳定性进行了探索，以用于随后的选择性转化，包括保留过氧化物基团的氨基过氧化物重排的第一个例子。氨基过氧化物中的氨基具有非常低的亲核性，不参与通常的胺烷基化和酰化反应。这些观察结果和 15 p与典型的二烷基胺相比，K a单位的碱性降低归因于强超共轭 n N →σ* C-O与两个反周面 C-O 键的相互作用。由于来自过氧化物氧的互补 n O →σ* C–N捐赠的弱点（“逆 α 效应”的结果），这种相互作用会消耗 NH 部分的电子密度，保护其免受氧化，并使其性质与酰胺相似。
• Methods for preparing 2,3,5,6-substituted 3h-pyrimidin-4-ones
  申请人：Shcherbakova Irina

  公开号：US20070161792A1

  公开（公告）日：2007-07-12

  Pyrimidinone compounds are disclosed. Methods of preparing the pyrimidinone compounds are also disclosed.

  本发明公开了嘧啶酮化合物。同时，本发明还公开了制备嘧啶酮化合物的方法。
• Studies on the α-acetylation of δ-valerolactone and ε-caprolactone
  作者：Jens Christoffers、Heiko Oertling、Peter Fischer、Wolfgang Frey

  DOI：10.1016/s0040-4020(03)00511-8

  日期：2003.5

  The synthetic approach to alpha-acetylated delta-valero- (7a) and epsilon-caprolactone (7b) is reported. While 7a was isolated in 21% yield from the respective iodoester 5a by an alkylation sequence involving transesterification and Finkelstein reaction, 7b was not obtained from 5b but the dimer 8. Also transesterification and olefin ring closing metathesis (RCM) failed to prepare 7b. RCM resulted in the dimeric lactone 10, showing that the formation of 14-membered rings is favored over that of seven-membered rings. A Mukaiyama-type Claisen reaction finally gave alpha-acetyl lactones 7a and 7b in practically useful quantity of about 10 g (62% yield): starting lactones 13a,b were converted to silylenolethers 14a,b, which were acetylated with acetic anhydride in presence of the Lewis acid catalyst TiCl4. However, acetylation depends on the addition sequence of starting materials: if the mixture of Ac2O/TiCl4 is added to 14b, lactone 7b can be further converted to give bis-oxepanonyl ethanols 15a,b. Both compounds 15 were characterized by X-ray crystallography and NMR. (C) 2003 Elsevier Science Ltd. All rights reserved.