α-methoxycarbonyl-α-(2-methylphenyl)-γ-methylidene-δ-valerolactone | 958000-86-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: α-methoxycarbonyl-α-(2-methylphenyl)-γ-methylidene-δ-valerolactone
• 英文别名: methyl 5-methylene-2-oxo-3-(o-tolyl)tetrahydro-2H-pyran-3-carboxylate；Methyl 5-methylidene-3-(2-methylphenyl)-2-oxooxane-3-carboxylate；methyl 5-methylidene-3-(2-methylphenyl)-2-oxooxane-3-carboxylate
• CAS: 958000-86-7
• 化学式: C₁₅H₁₆O₄
• 分子量: 260.29
• InChiKey: GFAIAZQCKDSXEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  α-methoxycarbonyl-α-(2-methylphenyl)-γ-methylidene-δ-valerolactone 在 四(三苯基膦)钯 、 对硝基苯酚 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 作用下， 以 乙醚 为溶剂， 以90 %的产率得到
  参考文献：
  名称：

  CN116239471

  摘要：

  公开号：
• 作为产物：
  描述：

  在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以71%的产率得到α-methoxycarbonyl-α-(2-methylphenyl)-γ-methylidene-δ-valerolactone
  参考文献：
  名称：

  钯催化的脱芳烃 [4 + 2]-环加成氢咔唑

  摘要：

  开发了一种通过高度非对映选择性钯催化的 [4 + 2]-环加成/脱芳构化 3-硝基吲哚来构建具有三个连续空间位阻立构中心（两个四元和一个三元）的氢咔唑的有效方法。3-硝基吲哚的环加成发生在环境条件下，1,4-两性离子中间体由 γ-亚甲基-δ-戊内酯原位生成。该方法的进一步综合效用通过产品可能的多方面转换得到证明。还探索了这种转化的催化不对称方面。

  DOI：

  10.1021/acs.joc.2c01869

文献信息

• Palladium-Catalyzed Synthesis of 4-Oxaspiro[2.4]heptanes via Central Attack of Oxygen Nucleophiles to π-Allylpalladium Intermediates
  作者：Ryo Shintani、Tomoaki Ito、Tamio Hayashi

  DOI：10.1021/ol300852v

  日期：2012.5.4

  cyclopropanation of γ-methylidene-δ-valerolactones with aromatic aldehydes has been developed to give 4-oxaspiro[2.4]heptanes with high selectivity. The site of nucleophilic attack to a π-allylpalladium intermediate has been controlled with a sterically demanding phosphine ligand. The course of the reaction is highly dependent on ligands and solvents, and selective formation of methylenetetrahydropyrans has

  已经开发了钯催化的γ-亚甲基-δ-戊内酯与芳族醛的脱羧环丙烷化反应，可高选择性地生成4-氧杂螺[2.4]庚烷。对π-烯丙基铝中间体的亲核攻击位点已通过空间需求的膦配体来控制。反应过程高度依赖于配体和溶剂，并且已经实现了亚甲基四氢吡喃的选择性形成。
• Gold and Palladium Relay Catalytic [4 + 4] Cycloadditions of Enynamides and γ-Methylene-δ-valerolactones: Diastereoselective Construction of Furan-Fused Azacyclooctanes
  作者：Yanfeng Gao、Hui Wang、Xiaoquan Chen、Yiyang Qiao、Zhiwei Miao

  DOI：10.1021/acs.joc.3c01114

  日期：2023.8.18

  subsequently participate in diastereoselective formal [4 + 4] cycloadditions with γ-methylene-δ-valerolactones. This strategy enables the rapid and efficient construction of a series of furan-fused azacyclooctanes with diverse substituents in good yields (63–97%) and a high level of diastereoselectivity (7:1 → 20:1 dr).

  我们报道了一种高效且非对映选择性的金和钯顺序中继催化系统，用于合成呋喃稠合八元杂环。采用一锅法，容易获得的烯酰胺进行环化，原位生成氮杂二烯，随后参与与 γ-亚甲基-δ-戊内酯的非对映选择性形式 [4 + 4] 环加成。该策略能够快速有效地构建一系列具有多种取代基的呋喃稠合氮杂环辛烷，且收率良好（63-97%），并且具有高水平的非对映选择性（7:1 → 20:1 dr）。
• Palladium-Catalyzed Decarboxylative [4 + 3] Cyclization of γ-Methylidene-δ-valerolactones with 1,1-Dicyanocyclopropanes
  作者：Ryo Shintani、Masataka Murakami、Takaoki Tsuji、Hideyuki Tanno、Tamio Hayashi

  DOI：10.1021/ol902326s

  日期：2009.12.17

  A palladium-catalyzed decarboxylative [4 + 3] cyclization of gamma-methylidene-delta-valerolactones with 1,1-dicyanocyclopropanes has been developed to produce cycloheptane derivatives in a convergent manner. This method can be applied to the synthesis of azepanes by reacting with aziridines, and their asymmetric variants have also been described. In addition, selective ring-expansion reactions can be achieved for certain gamma-methylidene-delta-valerolactones to give nondecarboxylated nine-membered lactones.
• γ-Methylidene-δ-valerolactones as a Coupling Partner for Cycloaddition:  Palladium-Catalyzed [4 + 3] Cycloaddition with Nitrones
  作者：Ryo Shintani、Masataka Murakami、Tamio Hayashi

  DOI：10.1021/ja073997f

  日期：2007.10.1

  A new type of reagent, gamma-methylidene-delta-valerolactones, has been devised, which acts as a four-carbon unit in a palladium-catalyzed cycloaddition reaction through the formation of a 1,4-zwitterionic species. The utility has been demonstrated in the context of stereoselective [4 + 3] cycloaddition with nitrones to provide highly functionalized 1,2-oxazepines, including the asymmetric variant with high enantioselectivity.
• Palladium-Catalyzed Synthesis of Spiro[2.4]heptanes:  Ligand-Dependent Position Control in the Nucleophilic Attack to a π-Allylpalladium Intermediate
  作者：Ryo Shintani、Soyoung Park、Tamio Hayashi

  DOI：10.1021/ja077236o

  日期：2007.12.1

  A palladium-catalyzed intermolecular cycloaddition of gamma-methylidene-delta-valerolactones with electron-deficient olefins has been developed for the synthesis of spiro[2.4]heptanes with high selectivity through a nucleophilic ring closure to the central carbon of a pi-allyipalladium intermediate. It was found that the course of the reaction is dependent on the ligand employed, and selective [4 + 2] cycloadditions can also be achieved by the use of a bulky monophosphine ligand.