(1S,4aS,4bR,8R,8aR,10aS)-8-methoxymethoxy-1,4a,8a-trimethyldodecahydrophenanthren-2(1H)-one | 1234031-59-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (1S,4aS,4bR,8R,8aR,10aS)-8-methoxymethoxy-1,4a,8a-trimethyldodecahydrophenanthren-2(1H)-one
• 英文别名: (1S,4aS,4bR,8R,8aR,10aS)-8-(methoxymethoxy)-1,4a,8a-trimethyl-3,4,4b,5,6,7,8,9,10,10a-decahydro-1H-phenanthren-2-one
• CAS: 1234031-59-4
• 化学式: C₁₉H₃₂O₃
• 分子量: 308.461
• InChiKey: WKVLDOHNYYAKQC-XZMJZXCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,4aS,4bR,8R,8aR,10aS)-8-methoxymethoxy-1,4a,8a-trimethyldodecahydrophenanthren-2(1H)-one 、 三甲基硅烷化重氮甲烷 在 三甲基铝 、 palladium diacetate 、 对苯醌 作用下， 以 hexanes 、 二氯甲烷 、 乙腈 为溶剂， 反应 36.0h， 以22%的产率得到(4R,4aR,6aS,7S,11aS,11bR)-4-(methoxymethoxy)-4a,7,11a-trimethyl-1,2,3,4,4a,5,6,6a,10,11,11a,11b-dodecahydro-9H-cyclohepta[a]naphthalen-9-one
  参考文献：
  名称：

  Synthesis of the western half of breviones C, D, F and G

  摘要：

  The enantioselective synthesis of the diterpenic moiety in the abeo-breviano skeleton is reported. The synthesis is carried out starting from 2-methyl-1,3-cyclohexanedione and EVK in eleven steps following a ring-expansion strategy once the tricyclic perhydrophenantrene skeleton has been obtained. A new Tiffeneau-Demjanov rearrangement under dark conditions is reported in which the insertion of the new methylene group is directed towards the most hindered side of the carbonyl group. This result is new and opposite to those reported in the literature under light (filtered or un-filtered wavelengths) conditions where insertion in the less hindered side is usually preferred. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.116
• 作为产物：
  描述：

  (1S,4aS,4bR,8R,8aR,10aS)-8-hydroxy-1,4a,8a-trimethyl-3,4,4b,5,6,7,8,9,10,10a-decahydro-1H-phenanthren-2-one 、 氯甲基甲基醚 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到(1S,4aS,4bR,8R,8aR,10aS)-8-methoxymethoxy-1,4a,8a-trimethyldodecahydrophenanthren-2(1H)-one
  参考文献：
  名称：

  Synthesis of the western half of breviones C, D, F and G

  摘要：

  The enantioselective synthesis of the diterpenic moiety in the abeo-breviano skeleton is reported. The synthesis is carried out starting from 2-methyl-1,3-cyclohexanedione and EVK in eleven steps following a ring-expansion strategy once the tricyclic perhydrophenantrene skeleton has been obtained. A new Tiffeneau-Demjanov rearrangement under dark conditions is reported in which the insertion of the new methylene group is directed towards the most hindered side of the carbonyl group. This result is new and opposite to those reported in the literature under light (filtered or un-filtered wavelengths) conditions where insertion in the less hindered side is usually preferred. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.116

文献信息

• Synthesis of the western half of breviones C, D, F and G
  作者：Francisco A. Macías、Ceferino Carrera、Nuria Chinchilla、Frank R. Fronczek、Juan C.G. Galindo

  DOI：10.1016/j.tet.2010.03.116

  日期：2010.6

  The enantioselective synthesis of the diterpenic moiety in the abeo-breviano skeleton is reported. The synthesis is carried out starting from 2-methyl-1,3-cyclohexanedione and EVK in eleven steps following a ring-expansion strategy once the tricyclic perhydrophenantrene skeleton has been obtained. A new Tiffeneau-Demjanov rearrangement under dark conditions is reported in which the insertion of the new methylene group is directed towards the most hindered side of the carbonyl group. This result is new and opposite to those reported in the literature under light (filtered or un-filtered wavelengths) conditions where insertion in the less hindered side is usually preferred. (C) 2010 Elsevier Ltd. All rights reserved.