2-phenyl-4-(trimethylsilyloxy)-2H-chromene | 54619-13-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: 2-phenyl-4-(trimethylsilyloxy)-2H-chromene
• 英文别名: Trimethyl[(2-phenyl-2H-1-benzopyran-4-yl)oxy]silane；trimethyl-[(2-phenyl-2H-chromen-4-yl)oxy]silane
• CAS: 54619-13-5
• 化学式: C₁₈H₂₀O₂Si
• 分子量: 296.441
• InChiKey: AYCODWUSYBSBDR-UHFFFAOYSA-N

物化性质

• 沸点：
  375.8±42.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.01
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-phenyl-4-(trimethylsilyloxy)-2H-chromene 在 二甲基二环氧乙烷 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 30.0h， 以85%的产率得到rac-trans-3-hydroxy-2-phenyl-3,4-dihydro-2H-chromen-4-one
  参考文献：
  名称：

  Dimethyldioxirane Oxidation of Titanium Enolates: Diastereoselective .alpha.-Hydroxylations

  摘要：

  The oxidation of titanium enolates, derived from a transmetalation reaction of the corresponding lithium enolates with (i-PrO)(3)TiCl, (Et(2)N)(3)TiCl, or Cp(2)TiCl(2), by dimethyldioxirane has been investigated. Furthermore, the diastereoselective hydroxylation of the chiral metal enolates, e.g., derived from camphor (1f), menthone (1g), flavanone (1h), and 2-benzylcyclopentanone (1i), by dimethyldioxirane has been examined. The diastereoselectivity of the oxygen transfer strongly depends on the metal partner coordinated to the enolate. The titanium enolates 4 resulted in much higher diastereoselectivities (up to 96% de) than the corresponding sodium enolates 5 and at least as high if not higher than the silyl enol ethers 6. Moreover, the aldol reaction of ester-derived sodium enolates with acetone, the unavoidable medium for dimethyldioxirane, could be totally suppressed by the use of the chlorotitanocene enolates 4. Thus, the oxidation of chiral titanium enolates by dimethyldioxirane represents a general, convenient, effective, and chemo- and diastereoselective synthesis of alpha-hydroxy carbonyl compounds.

  DOI：

  10.1021/jo00088a015
• 作为产物：
  描述：

  三甲基氯硅烷 、 黄烷酮 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 5.5h， 以54%的产率得到2-phenyl-4-(trimethylsilyloxy)-2H-chromene
  参考文献：
  名称：

  β-重氮羰基化合物：合成及其Rh（II）催化的1,3 CH插入

  摘要：

  本文中，我们描述了使用重氮甲基取代的高价碘试剂对酮甲硅烷基烯醇醚进行的首次亲电重氮甲基化，该试剂可访问不常见的β-重氮羰基化合物。通过发现罕见的Rh催化的分子内1,3 C-H卡宾插入导致复杂的环丙烷具有出色的立体控制，这一未开发的重氮化合物类在开发新反应中的潜力得到了证明。

  DOI：

  10.1002/anie.202015077

文献信息

• LI, LIANG-HU;RUI, YUANJIN, BEHJTSZIN DASYUEH SYUEHBAO, 26,(1990) N, S. 421-428
  作者：LI, LIANG-HU、RUI, YUANJIN

  DOI：——

  日期：——
• β‐Diazocarbonyl Compounds: Synthesis and their Rh(II)‐Catalyzed 1,3 C−H Insertions
  作者：Liyin Jiang、Zhaofeng Wang、Melanie Armstrong、Marcos G. Suero

  DOI：10.1002/anie.202015077

  日期：2021.3.8

  of ketone silyl enol ethers with diazomethyl‐substituted hypervalent iodine reagents that gives access to unusual β‐diazocarbonyl compounds. The potential of this unexplored class of diazo compounds for the development of new reactions was demonstrated by the discovery of a rare Rh‐catalyzed intramolecular 1,3 C−H carbene insertion that led to complex cyclopropanes with excellent stereocontrol.

  本文中，我们描述了使用重氮甲基取代的高价碘试剂对酮甲硅烷基烯醇醚进行的首次亲电重氮甲基化，该试剂可访问不常见的β-重氮羰基化合物。通过发现罕见的Rh催化的分子内1,3 C-H卡宾插入导致复杂的环丙烷具有出色的立体控制，这一未开发的重氮化合物类在开发新反应中的潜力得到了证明。
• Dimethyldioxirane Oxidation of Titanium Enolates: Diastereoselective .alpha.-Hydroxylations
  作者：Waldemar Adam、Michael Mueller、Frank Prechtl

  DOI：10.1021/jo00088a015

  日期：1994.5

  The oxidation of titanium enolates, derived from a transmetalation reaction of the corresponding lithium enolates with (i-PrO)(3)TiCl, (Et(2)N)(3)TiCl, or Cp(2)TiCl(2), by dimethyldioxirane has been investigated. Furthermore, the diastereoselective hydroxylation of the chiral metal enolates, e.g., derived from camphor (1f), menthone (1g), flavanone (1h), and 2-benzylcyclopentanone (1i), by dimethyldioxirane has been examined. The diastereoselectivity of the oxygen transfer strongly depends on the metal partner coordinated to the enolate. The titanium enolates 4 resulted in much higher diastereoselectivities (up to 96% de) than the corresponding sodium enolates 5 and at least as high if not higher than the silyl enol ethers 6. Moreover, the aldol reaction of ester-derived sodium enolates with acetone, the unavoidable medium for dimethyldioxirane, could be totally suppressed by the use of the chlorotitanocene enolates 4. Thus, the oxidation of chiral titanium enolates by dimethyldioxirane represents a general, convenient, effective, and chemo- and diastereoselective synthesis of alpha-hydroxy carbonyl compounds.