(-)-menthyl γ-(2-cyclohexenyloxy)-α-diazo-β-ketoester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (-)-menthyl γ-(2-cyclohexenyloxy)-α-diazo-β-ketoester
• 英文别名: Methyl 4-cyclohex-2-en-1-yloxy-2-diazo-3-oxobutanoate；methyl 4-cyclohex-2-en-1-yloxy-2-diazo-3-oxobutanoate
• 化学式: C₁₁H₁₄N₂O₄
• 分子量: 238.243
• InChiKey: SYWHCKNJXHYYDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-menthyl γ-(2-cyclohexenyloxy)-α-diazo-β-ketoester 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 以65%的产率得到(Z)-4-[(-)-menthoxycarbonylmethylidene]-2-(pent-1-en-1,5-diyl)-1,3-dioxolane
  参考文献：
  名称：

  Ruthenium(II) Porphyrin Catalyzed Formation of (Z)-4-Alkyloxycarbonyl- methylidene-1,3-dioxolanes from γ-Alkoxy-α-diazo-β-ketoesters

  摘要：

  [GRAPHICS]Ruthenum(II) porphyrins and dirhodium(II) acetate catalyze cyclization of gamma-alkoxy-alpha-diazo-beta-ketoesters to (Z)-4-(alkyloxycarbonylmethylidene)-1,3-dioxolanes selectively (ca. 68% yield) with no formation of 3(2H)-furanones. Reacting a diazo ketoester with [Ru-II(TTP)(CO)] [H2TTP = meso-tetrakis(p-tolyl) porphyrin] in toluene afforded a ruthenium carbenoid complex, which has been isolated and spectroscopically characterized. A mechanism involving hydrogen atom migration from the C-H bond to the ruthenium carbenoid is proposed.

  DOI：

  10.1021/ol010283f
• 作为产物：
  描述：

  2-环己烯醇 在 sodium hydride 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 生成 (-)-menthyl γ-(2-cyclohexenyloxy)-α-diazo-β-ketoester
  参考文献：
  名称：

  Ruthenium(II) Porphyrin Catalyzed Formation of (Z)-4-Alkyloxycarbonyl- methylidene-1,3-dioxolanes from γ-Alkoxy-α-diazo-β-ketoesters

  摘要：

  [GRAPHICS]Ruthenum(II) porphyrins and dirhodium(II) acetate catalyze cyclization of gamma-alkoxy-alpha-diazo-beta-ketoesters to (Z)-4-(alkyloxycarbonylmethylidene)-1,3-dioxolanes selectively (ca. 68% yield) with no formation of 3(2H)-furanones. Reacting a diazo ketoester with [Ru-II(TTP)(CO)] [H2TTP = meso-tetrakis(p-tolyl) porphyrin] in toluene afforded a ruthenium carbenoid complex, which has been isolated and spectroscopically characterized. A mechanism involving hydrogen atom migration from the C-H bond to the ruthenium carbenoid is proposed.

  DOI：

  10.1021/ol010283f

文献信息

• Ruthenium(II) Porphyrin Catalyzed Formation of (<i>Z</i>)-4-Alkyloxycarbonyl- methylidene-1,3-dioxolanes from <i>γ</i>-Alkoxy-<i>α</i>-diazo-<i>β</i>-ketoesters
  作者：Shi-Long Zheng、Wing-Yiu Yu、Chi-Ming Che

  DOI：10.1021/ol010283f

  日期：2002.3.1

  [GRAPHICS]Ruthenum(II) porphyrins and dirhodium(II) acetate catalyze cyclization of gamma-alkoxy-alpha-diazo-beta-ketoesters to (Z)-4-(alkyloxycarbonylmethylidene)-1,3-dioxolanes selectively (ca. 68% yield) with no formation of 3(2H)-furanones. Reacting a diazo ketoester with [Ru-II(TTP)(CO)] [H2TTP = meso-tetrakis(p-tolyl) porphyrin] in toluene afforded a ruthenium carbenoid complex, which has been isolated and spectroscopically characterized. A mechanism involving hydrogen atom migration from the C-H bond to the ruthenium carbenoid is proposed.