2,6--3,7-dioxobicyclo<3.3.0>octane | 138253-19-7

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 木脂素内酯
• 英文名称: 2,6--3,7-dioxobicyclo<3.3.0>octane
• 英文别名: 2,6-Bis<3,4-(methylenedioxy)phenyl>-3,7-dioxobicyclo<3.3.0>octane；(1S,3aS,4S,6aS)-1,4-bis(1,3-benzodioxol-5-yl)-1,3,3a,4,6,6a-hexahydropentalene-2,5-dione
• CAS: 138253-19-7
• 化学式: C₂₂H₁₈O₆
• 分子量: 378.381
• InChiKey: LBXWATKMKCTVFL-HCIHMXRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  28.0
• 可旋转键数：
  2.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2,6--3,7-dioxobicyclo<3.3.0>octane 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 240.0h， 以28%的产率得到2,7--3,8-dioxabicyclo<4.4.0>decane-4,9-dione
  参考文献：
  名称：

  A new stereo- and regioselective synthesis of (±)-sesamin involving a β-scission of alkoxyl radicals as the key step1

  摘要：

  A new stereo- and regioselective synthesis of (+/-)-sesamin (a representative lignan) based on our general method for the transformation of a cyclopentanone ring into a tetrahydrofuran ring involving a regioselective beta-scission of the alkoxyl radicals is reported.

  DOI：

  10.1016/s0040-4039(00)79448-2
• 作为产物：
  描述：

  2,6-Dibenzyl 2,6-bis<(3,4-methylenedioxy)phenyl>-3,7-dioxobicyclo<3.3.0>octane-2,6-dicarboxylate 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 20.0h， 以74%的产率得到2,6--3,7-dioxobicyclo<3.3.0>octane
  参考文献：
  名称：

  A new stereo- and regioselective synthesis of (±)-sesamin involving a β-scission of alkoxyl radicals as the key step1

  摘要：

  A new stereo- and regioselective synthesis of (+/-)-sesamin (a representative lignan) based on our general method for the transformation of a cyclopentanone ring into a tetrahydrofuran ring involving a regioselective beta-scission of the alkoxyl radicals is reported.

  DOI：

  10.1016/s0040-4039(00)79448-2

文献信息

• Photoinduced Molecular Transformations. 157. A New Stereo- and Regioselective Synthesis of 2,6-Diaryl-3,7-dioxabicyclo[3.3.0]octane Lignans Involving a .beta.-Scission of Alkoxyl Radicals as the Key Step. New Total Syntheses of (.+-.)-Sesamin, (.+-.)-Eudesmin, and (.+-.)-Yangambin
  作者：Hiroshi Suginome、Masataka Ishikawa、Kaoru Yorita、Noriaki Shimoyama、Takahiro Sasaki、Kazuhiko Orito

  DOI：10.1021/jo00115a021

  日期：1995.5

  New total syntheses of naturally occurring 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans, (+/-)-sesamin and (+/-)-eudesmin, and the first total synthesis of (+/-)-yangambin were achieved according to a general method devised by Suginome and colleagues for replacing the carbonyl group of the cyclopentanone ring with an oxygen atom to give a corresponding tetrahydrofuran ring involving a regioselective beta-scission of alkoxyl radicals; arylation of dimethyl, diallyl, or dibenzyl 3,7-dioxobicyclo[3.3.0]octane-2,6-dicarbonate (18 and 19a,b) with aryllead triacetate 9a-c, followed by dealkoxycarbonylation of the resulting arylated product 20a-f, gave 2,6-diaryl-3,7-dioxobicyclo-[3.3.0]octane 21a-c. A regioselective Baeyer-Villiger oxidation of 21a-e with m-CPBA-NaHCO3 or -K2CO3 gave the corresponding delta-lactone 22a-c, which was reduced with DIBAL to give the corresponding lactol 23a-c. The irradiation of a solution of the hypoiodite of 23a-c, generated in situ with mercury(II) oxide-iodine, in benzene with Pyrex-filtered light resulted in a regioselective beta-scission of the corresponding alkoxyl radical to give iodo formate 24a-c. Heating 24a-c in MeOH with NaBH4 gave (+/-)-sesamin (25a), (+/-)-eudesmin (25b), or (+/-)-yangambin (25c).