(1S*,4R*,5R*)-methyl 2,2-ethylenedioxy-5-(2-methoxymethoxyethyl)-4-methyl-7-oxobicyclo[3.2.1]octane-6-carboxylate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S*,4R*,5R*)-methyl 2,2-ethylenedioxy-5-(2-methoxymethoxyethyl)-4-methyl-7-oxobicyclo[3.2.1]octane-6-carboxylate
• 英文别名: methyl (1'S,4'S,5'R)-5'-[2-(methoxymethoxy)ethyl]-4'-methyl-7'-oxospiro[1,3-dioxolane-2,2'-bicyclo[3.2.1]octane]-6'-carboxylate
• 化学式: C₁₇H₂₆O₇
• 分子量: 342.389
• InChiKey: WXQVUNXEUYGDSS-BEHMWDDESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1S*,4R*,5R*)-methyl 2,2-ethylenedioxy-5-(2-methoxymethoxyethyl)-4-methyl-7-oxobicyclo[3.2.1]octane-6-carboxylate 在 咪唑 、 六甲基磷酰三胺 、 三氢化钐 、 lithium aluminium tetrahydride 、 2-甲基-2-丁烯 、 dimethyl sulfide borane 、 potassium tert-butylate 、 碘 、 sodium hydride 、 碘乙烷 、 三苯基膦 作用下， 以 四氢呋喃 、 吡啶 、 六甲基磷酰三胺 、 甲苯 、 乙腈 为溶剂， 反应 60.75h， 生成 (1S*,7R*,8R*)-7-(2-methoxymethoxyethyl)-8-methyl-6-methylidenebicyclo[5.3.1]undecan-2,10-dione 10-ethylene acetal
  参考文献：
  名称：

  Some Aspects of Palladium-Catalyzed Cycloalkenylation:  Developments of Environmentally Benign Catalytic Conditions and Demonstration of Tandem Cycloalkenylation

  摘要：

  The influences of catalysts, substituent groups, and solvents on the palladium-catalyzed cycloalkenylation of cross-conjugated silyl enol ethers of 2-tert-butyldimethylsiloxy-5-(2-propenyl)-1,3-cyclohexadiene derivatives have been investigated. The catalytic reaction proceeded smoothly, even in aqueous media. The product ratios were influenced by the structure of substrates as well as solvents. In addition, it was found that the reaction is applicable to a tandem cyclization for the construction of cedrane skeleton.

  DOI：

  10.1021/jo011169d
• 作为产物：
  描述：

  (1S*,4R*,5R*)-5-(2-methoxymethoxyethyl)-4-methyl-7-methylidenebicyclo[3.2.1]octan-2-one 在 六甲基磷酰三胺 、 sodium periodate 、 四氧化锇 、 4-甲基苯磺酸吡啶 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 水 、 苯 为溶剂， 反应 33.0h， 生成 (1S*,4R*,5R*)-methyl 2,2-ethylenedioxy-5-(2-methoxymethoxyethyl)-4-methyl-7-oxobicyclo[3.2.1]octane-6-carboxylate
  参考文献：
  名称：

  Some Aspects of Palladium-Catalyzed Cycloalkenylation:  Developments of Environmentally Benign Catalytic Conditions and Demonstration of Tandem Cycloalkenylation

  摘要：

  The influences of catalysts, substituent groups, and solvents on the palladium-catalyzed cycloalkenylation of cross-conjugated silyl enol ethers of 2-tert-butyldimethylsiloxy-5-(2-propenyl)-1,3-cyclohexadiene derivatives have been investigated. The catalytic reaction proceeded smoothly, even in aqueous media. The product ratios were influenced by the structure of substrates as well as solvents. In addition, it was found that the reaction is applicable to a tandem cyclization for the construction of cedrane skeleton.

  DOI：

  10.1021/jo011169d

文献信息

• Application of palladium-catalyzed cycloalkenylation reaction to terpenoid synthesis—novel approach to tricyclo[5.3.1.02,6]undecane derivative and its transformation into bicyclo[5.3.1]undecane ring system
  作者：Masahiro Toyota*、Marcellino Rudyanto、Masataka Ihara

  DOI：10.1016/s0040-4039(00)01609-9

  日期：2000.11

  A novel synthesis of the tricyclo[5.3.1.02,6]undecane compound 16, basic carbon skeleton of gymnomitrane class of sesquiterpenoids, and the transformation into the bicyclo[5.3.1]undecane derivative 18, the AB carbon framework of taxol (6), have been achieved. Beginning with the bicyclo[3.2.1]octane ring system 2, prepared from the cross-conjugated silyl enol ether 1 employing palladium-catalyzed cycloalkenylation

  三环[5.3.1.0 2,6 ]十一烷化合物16，裸子萜类香茅类基本碳骨架的新颖合成，以及向紫杉醇的AB碳骨架的双环[5.3.1]十一烷衍生物18的转化（6），已经实现。从使用钯催化的环烯基化反应的交叉共轭甲硅烷基烯醇醚1制备的双环[3.2.1]辛烷环体系2开始，使用sa合成了三环[5.3.1.0 2,6 ]十一烷环体系16促进15的还原环化。转换后16对于羟基甲苯磺酸酯17，碱性处理17得到所需的双环[5.3.1]十一烷衍生物18。有趣的是，还与18一起获得了高张力的氧杂环丁烷19。