(1R,4S,6R)-1,3,3-trimethyl-4-(prop-1-en-2-yl)-7-oxa-bicyclo[4.1.0]heptan-2-one | 1219444-09-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1R,4S,6R)-1,3,3-trimethyl-4-(prop-1-en-2-yl)-7-oxa-bicyclo[4.1.0]heptan-2-one
• 英文别名: (1R,4S,6R)-4-isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one；(1r,4s,6r)-4-Isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one；(1R,4S,6R)-1,3,3-trimethyl-4-prop-1-en-2-yl-7-oxabicyclo[4.1.0]heptan-2-one
• CAS: 1219444-09-3
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: JJBKKJCQCOPPBR-YGOYTEALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4S,6R)-1,3,3-trimethyl-4-(prop-1-en-2-yl)-7-oxa-bicyclo[4.1.0]heptan-2-one 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 20.0h， 生成 (1R,2R,4S,6R)-4-isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]hept-2-yl acetate
  参考文献：
  名称：

  Efficient synthesis of (1R,4S,6R)-4-Isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one

  摘要：

  A simple and convenient one-pot synthesis of (1R,4S,6R)-4-isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one was developed consisting in a thermodynamic methylation of carvone (NaH, MeI, THF, 20 degrees C) followed by the epoxidation with alkalinized hydrogen peroxide. The reduction of the obtained epoxyketone with sodium borohydride proceeded stereoselectively to give a beta-alcohol. The attempts to convert its isopropenyl fragment into an acetate group by a rearrangement of products or intermediates of the oxidative fragmentation resulted only in obtaining intermediate acyl derivatives.

  DOI：

  10.1134/s1070428011020047
• 作为产物：
  描述：

  (R)-Carvone 、 碘甲烷 在 六甲基磷酰三胺 、 sodium hydride 、 双氧水 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 20.25h， 以50%的产率得到(1R,4S,6R)-1,3,3-trimethyl-4-(prop-1-en-2-yl)-7-oxa-bicyclo[4.1.0]heptan-2-one
  参考文献：
  名称：

  Efficient synthesis of (1R,4S,6R)-4-Isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one

  摘要：

  A simple and convenient one-pot synthesis of (1R,4S,6R)-4-isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one was developed consisting in a thermodynamic methylation of carvone (NaH, MeI, THF, 20 degrees C) followed by the epoxidation with alkalinized hydrogen peroxide. The reduction of the obtained epoxyketone with sodium borohydride proceeded stereoselectively to give a beta-alcohol. The attempts to convert its isopropenyl fragment into an acetate group by a rearrangement of products or intermediates of the oxidative fragmentation resulted only in obtaining intermediate acyl derivatives.

  DOI：

  10.1134/s1070428011020047

文献信息

• An Expeditious Route to 1α,25-Dihydroxyvitamin D₃and Its Analogues by an Aqueous Tandem Palladium-Catalyzed A-Ring Closure and Suzuki Coupling to the C/D Unit
  作者：Pranjal Gogoi、Rita Sigüeiro、Silvina Eduardo、Antonio Mouriño

  DOI：10.1002/chem.200902972

  日期：2010.2.1

  mild, general, and highly stereoselective Pd0‐catalyzed cascade to the triene system of the hormone 1α,25‐dihydroxyvitamin D3 and six representative analogues is reported. The intramolecular cyclization of an enol–triflate (lower fragment) followed in situ by Suzuki–Miyaura coupling with an alkenyl boronic ester (upper fragment, also efficiently prepared by Pd0‐catalyzed coupling) in equimolar amounts

  每日维生素：有轻度，一般和高度立体选择性的Pd 0催化与1α，25-二羟基维生素D 3和6种代表性类似物的三烯系统级联。在质子化条件下等摩尔量的烯醇-三氟甲磺酸分子的分子内环化（下片段），然后是铃木-宫浦（Suzuki-Miyaura）与烯基硼酸酯（上片段，也可通过Pd 0催化偶联有效制备）原位合成用于生物测试的少量新维生素D类似物（请参阅计划）。
• Efficient synthesis of (1R,4S,6R)-4-Isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one
  作者：N. K. Selezneva、F. A. Gimalova、R. F. Valeev、M. S. Miftakhov

  DOI：10.1134/s1070428011020047

  日期：2011.2

  A simple and convenient one-pot synthesis of (1R,4S,6R)-4-isopropenyl-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one was developed consisting in a thermodynamic methylation of carvone (NaH, MeI, THF, 20 degrees C) followed by the epoxidation with alkalinized hydrogen peroxide. The reduction of the obtained epoxyketone with sodium borohydride proceeded stereoselectively to give a beta-alcohol. The attempts to convert its isopropenyl fragment into an acetate group by a rearrangement of products or intermediates of the oxidative fragmentation resulted only in obtaining intermediate acyl derivatives.