methyl (4S,5R)-α-diazo-2,2-dimethyl-5-ethyl-1,3-dioxanepropionate | 164228-89-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (4S,5R)-α-diazo-2,2-dimethyl-5-ethyl-1,3-dioxanepropionate
• 英文别名: methyl 2-diazo-3-[(4S,5R)-5-ethyl-2,2-dimethyl-1,3-dioxan-4-yl]propanoate
• CAS: 164228-89-1
• 化学式: C₁₂H₂₀N₂O₄
• 分子量: 256.302
• InChiKey: QRDVTFNOGYHOLC-SCZZXKLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  46.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (4S,5R)-α-diazo-2,2-dimethyl-5-ethyl-1,3-dioxanepropionate 在 吡啶 、 lithium aluminium tetrahydride 、 辛酸铑 、 三丁基膦 、 四丁基碘化铵 、 sodium hydride 、 potassium carbonate 、 对甲苯磺酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 54.74h， 生成 (2S,3S,3aS,6S,8aR,9S,9aR)-2-Benzyloxymethyl-3,6-dimethyl-9-phenylsulfanylmethyl-dodecahydro-4a-aza-cyclopenta[b]naphthalene
  参考文献：
  名称：

  Highly Diastereoselective Cyclopentane Construction: Enantioselective Synthesis of the Dendrobatid Alkaloid 251F

  摘要：

  We report the first total synthesis, and thus structural confirmation, of the dendrobatid alkaloid 251F (1), based on the retrosynthetic analysis illustrated (1 <-- <-- 4). Key observations in this synthesis are that both the Rh-mediated cyclization of 1 and the anionic cyclization of 2 proceed with excellent diastereoselectivity.

  DOI：

  10.1021/ja00126a015
• 作为产物：
  描述：

  methyl (4S,5R)-2,2-dimethyl-5-ethyl-1,3-dioxane-4-propionate 在 甲醇 、 p-nitrobenzenesulfonyl azide 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 13.5h， 生成 methyl (4S,5R)-α-diazo-2,2-dimethyl-5-ethyl-1,3-dioxanepropionate
  参考文献：
  名称：

  Predicting the Diastereoselectivity of Rh-Mediated Intramolecular C−H Insertion

  摘要：

  Rhodium-mediated cyclization of the alpha-diazo ester 1 proceeds with high diastereoselectivity, to give the trisubstituted cyclopentane 5. A computational model (ZINDO and Molecular Mechanics) based on our current mechanistic understanding of the reaction is presented. This model correctly predicts the dominant diastereomer from the cyclization of 1 and the eight (Table 2) other alpha-diazo esters studied thus far.

  DOI：

  10.1021/ja9515213

文献信息

• Predicting the Diastereoselectivity of Rh-Mediated Intramolecular C−H Insertion
  作者：Douglass F. Taber、Kamfia K. You、Arnold L. Rheingold

  DOI：10.1021/ja9515213

  日期：1996.1.1

  Rhodium-mediated cyclization of the alpha-diazo ester 1 proceeds with high diastereoselectivity, to give the trisubstituted cyclopentane 5. A computational model (ZINDO and Molecular Mechanics) based on our current mechanistic understanding of the reaction is presented. This model correctly predicts the dominant diastereomer from the cyclization of 1 and the eight (Table 2) other alpha-diazo esters studied thus far.
• Highly Diastereoselective Cyclopentane Construction: Enantioselective Synthesis of the Dendrobatid Alkaloid 251F
  作者：Douglass F. Taber、Kamfia K. You

  DOI：10.1021/ja00126a015

  日期：1995.5

  We report the first total synthesis, and thus structural confirmation, of the dendrobatid alkaloid 251F (1), based on the retrosynthetic analysis illustrated (1 <-- <-- 4). Key observations in this synthesis are that both the Rh-mediated cyclization of 1 and the anionic cyclization of 2 proceed with excellent diastereoselectivity.