(Z)-2-diazonio-1-methoxy-1-oxo-6-prop-2-enoxyhex-2-en-3-olate

• 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: (Z)-2-diazonio-1-methoxy-1-oxo-6-prop-2-enoxyhex-2-en-3-olate
• 化学式: C₁₀H₁₄N₂O₄
• 分子量: 226.232
• InChiKey: YEDYFQJZDOYEBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (Z)-2-diazonio-1-methoxy-1-oxo-6-prop-2-enoxyhex-2-en-3-olate 在 Rh2<(S)-N-phthaloyl-tert-leucinate>4 作用下， 以 正己烷 为溶剂， 以54%的产率得到2-allyl-2-methoxycarbonyl-3-oxotetrahydropyran
  参考文献：
  名称：

  重氮羰基化合物催化不对称的氧鎓叶立德-[2,3]σ重排：在Rh（II）羧酸盐中首次使用C 2对称性

  摘要：

  已经合成了几种新的手性铑（II）催化剂，作为重氮羰基底物的不对称氧代内鎓盐-[2,3]σ重排的催化剂进行评估。衍生自（S）-叔亮氨酸的催化剂提供了ee为60％的手性苯并呋喃酮衍生物。

  DOI：

  10.1016/s0040-4039(97)01003-4

文献信息

• Intramolecular generation and [2,3]-sigmatropic rearrangement of oxonium ylides
  作者：Michael C. Pirrung、John A. Werner

  DOI：10.1021/ja00279a076

  日期：1986.9
• Electronic Effects in Dirhodium(II) Carboxylates. Linear Free Energy Relationships in Catalyzed Decompositions of Diazo Compounds and CO and Isonitrile Complexation
  作者：Michael C. Pirrung、Andrew T. Morehead

  DOI：10.1021/ja00099a017

  日期：1994.10

  A linear free energy analysis of substituent effects in rhodium carboxylate complexes has been conducted. Two reactions of diazo compounds involving intramolecular competition between (1) O-ylide formation and secondary C-H insertion, and (2) tertiary C-H and primary C-H insertion were studied as well as complexation effects on the IR frequencies of CO and tert-butyl isocyanide. Aliphatic and aromatic carboxylate complexes were included. Regression equations that describe these processes include contributions from sigma(alpha) (polarizability) and sigma(F) (field effects) and, for the benzoates, sigma(R) (resonance). Complexes that deviate from the LFER include rhodium trifluoroacetate and rhodium triptycenecarboxylate, and their behavior was explained through (partial) release of the free carbene. The effect of ligand polarizability on selectivity in these reactions was interpreted as evidence for the importance of backbonding from rhodium to the carbene carbon in the product-determining step. The ability of these complexes to backbond was shown through the complexation study. Higher selectivity with increasing ability to backbond is analogous to other carbenes such as difluorocarbene. Increased selectivity engendered by backbonding could occur by facilitating the reversal of an intermediate complex between the carbenoid and the C-H bond undergoing insertion. Increased selectivity engendered by field effects and polarizability could be explained by increased selectivity for electron-rich sites.
• PIRRUNG M. C.; WERNER J. A., J. AMER. CHEM. SOC., 108,(1986) N 19, 6060-6062
  作者：PIRRUNG M. C.、 WERNER J. A.

  DOI：——

  日期：——