2-<(methoxycarbonyl)oxy>-3-<(trimethylsilyl)methyl>-3-butenoic acid | 135619-58-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: 2-<(methoxycarbonyl)oxy>-3-<(trimethylsilyl)methyl>-3-butenoic acid
• 英文别名: 2-methoxycarbonyloxy-3-(trimethylsilylmethyl)but-3-enoic acid
• CAS: 135619-58-8
• 化学式: C₁₀H₁₈O₅Si
• 分子量: 246.335
• InChiKey: UTNGVHQENXRXOO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  16.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  72.83
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-<(methoxycarbonyl)oxy>-3-<(trimethylsilyl)methyl>-3-butenoic acid 在 4-二甲氨基吡啶 、 palladium diacetate 、 三异丙基亚磷酸酯 、 N,N'-二环己基碳二亚胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 2.52h， 生成 (1S*,4S*,8R*,11S*)-10-methylene-8-(phenylsulfonyl)-2-oxo-3-oxatricyclo<6.2.1.04,11>undecane
  参考文献：
  名称：

  Intramolecular palladium-catalyzed cycloadditions with a cleavable tether

  摘要：

  A facile synthesis of 2-(acyloxy)-3-methylene-4-(trimethylsilyl)butyric acids evolves from the use of tris(phenylthio)acetaldehyde as a practical glyoxylic ester equivalent. Introduction of the bifunctional donor of a [3 + 2] cycloaddition proceeds simply by esterification of an alcohol possessing TMM-PdL2 acceptor units. The synthetic flexibility of the sulfone leads to the choice of alpha, beta-unsaturated sulfones as the acceptors. Palladium-catalyzed cycloadditions proceed smoothly at temperatures as low as room temperature. Depending upon the substitution pattern and especially the conformation of the substrate, tethering the ester containing the bifunctional TMM unit at the carbon allylic to the acceptor provides substrates that predominantly to exclusively undergo cycloaddition rather than processes dominated by an alternative Pd(0)-catalyzed ionization. Since the ester linkage is easily cleaved, this sequence serves as a convenient strategy for controlled TMM-PdL2 cycloadditions. For example, the diastereofacial selectivity of this intramolecular process involves attack syn to the allylic oxygen in a six- or seven-membered-ring acceptor but anti to this oxygen in an intermolecular process. A diastereocontrolled cyclopentenone annulation is developed. Interestingly, the intramolecular cycloaddition of eight- and twelve-membered rings proceeds anti to the allylic oxygen. As an aside, the indefinite shelf life of the crystalline tris(phenylthio)acetaldehyde makes it a convenient glyoxylate synthon.

  DOI：

  10.1021/ja00019a037
• 作为产物：
  描述：

  1,1,1-tris(phenylthio)-2-<(methoxycarbonyl)oxy>-3-<(trimethylsilyl)methyl>-3-butene 在 水 、 silver trifluoroacetate 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 以64%的产率得到2-<(methoxycarbonyl)oxy>-3-<(trimethylsilyl)methyl>-3-butenoic acid
  参考文献：
  名称：

  Intramolecular palladium-catalyzed cycloadditions with a cleavable tether

  摘要：

  A facile synthesis of 2-(acyloxy)-3-methylene-4-(trimethylsilyl)butyric acids evolves from the use of tris(phenylthio)acetaldehyde as a practical glyoxylic ester equivalent. Introduction of the bifunctional donor of a [3 + 2] cycloaddition proceeds simply by esterification of an alcohol possessing TMM-PdL2 acceptor units. The synthetic flexibility of the sulfone leads to the choice of alpha, beta-unsaturated sulfones as the acceptors. Palladium-catalyzed cycloadditions proceed smoothly at temperatures as low as room temperature. Depending upon the substitution pattern and especially the conformation of the substrate, tethering the ester containing the bifunctional TMM unit at the carbon allylic to the acceptor provides substrates that predominantly to exclusively undergo cycloaddition rather than processes dominated by an alternative Pd(0)-catalyzed ionization. Since the ester linkage is easily cleaved, this sequence serves as a convenient strategy for controlled TMM-PdL2 cycloadditions. For example, the diastereofacial selectivity of this intramolecular process involves attack syn to the allylic oxygen in a six- or seven-membered-ring acceptor but anti to this oxygen in an intermolecular process. A diastereocontrolled cyclopentenone annulation is developed. Interestingly, the intramolecular cycloaddition of eight- and twelve-membered rings proceeds anti to the allylic oxygen. As an aside, the indefinite shelf life of the crystalline tris(phenylthio)acetaldehyde makes it a convenient glyoxylate synthon.

  DOI：

  10.1021/ja00019a037