4a-allyl-1,2,4,4a-tetrahydrospiro[carbazole-3,4'-[1,2]dioxolane] | 1345321-96-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 4a-allyl-1,2,4,4a-tetrahydrospiro[carbazole-3,4'-[1,2]dioxolane]
• 英文别名: 4'a-prop-2-enylspiro[1,3-dioxolane-2,3'-2,4-dihydro-1H-carbazole]
• CAS: 1345321-96-1
• 化学式: C₁₇H₁₉NO₂
• 分子量: 269.343
• InChiKey: SCJXITSYOLBDFN-UHFFFAOYSA-N

物化性质

• 沸点：
  390.2±42.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4a-allyl-1,2,4,4a-tetrahydrospiro[carbazole-3,4'-[1,2]dioxolane] 在 三乙烯二胺 、 potassium osmate(VI) dihydrate 、 potassium hexacyanoferrate(III) 、 sodium periodate 、 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 sodium hydride 、 potassium carbonate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 丙酮 、 乙腈 、 叔丁醇 为溶剂， 反应 45.0h， 生成 methyl (1R,9R,11S,12E)-12-ethylidene-18-oxo-8,14-diazapentacyclo[9.5.2.01,9.02,7.09,14]octadeca-2,4,6-triene-8-carboxylate
  参考文献：
  名称：

  A Concise Total Synthesis of (±)-Minfiensine

  摘要：

  A concise total synthesis of (+/-)-minfiensine using all conventional methods and starting from commercial materials has been completed. The synthesis features a Fischer indole synthesis, a Heck alkylation of an intermediate ketone enolate, conversion of a ketone carbonyl into an epoxide, and transformation of the latter into an allylic alcohol.

  DOI：

  10.1021/ol2027224
• 作为产物：
  描述：

  苯肼 在 tris-(dibenzylideneacetone)dipalladium(0) 、 三苯基膦 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 17.17h， 生成 4a-allyl-1,2,4,4a-tetrahydrospiro[carbazole-3,4'-[1,2]dioxolane]
  参考文献：
  名称：

  A Concise Total Synthesis of (±)-Minfiensine

  摘要：

  A concise total synthesis of (+/-)-minfiensine using all conventional methods and starting from commercial materials has been completed. The synthesis features a Fischer indole synthesis, a Heck alkylation of an intermediate ketone enolate, conversion of a ketone carbonyl into an epoxide, and transformation of the latter into an allylic alcohol.

  DOI：

  10.1021/ol2027224

文献信息

• Palladium Catalyzed Decarboxylative Rearrangement of <i>N</i>-Alloc Indoles
  作者：Jun Chen、Matthew J. Cook

  DOI：10.1021/ol400110c

  日期：2013.3.1

  A highly efficient palladium catalyzed decarboxylative allylic rearrangement of alloc indoles has been developed. This can also be combined with a Suzuki–Miyaura cross-coupling reaction in a single pot transformation. Substituted alloc groups and benzylic variants have also been demonstrated alongside promising initial results on the enantioselective variant.

  已经开发了分配吲哚的高效钯催化的脱羧烯丙基重排。也可以在单个罐转化中将其与Suzuki-Miyaura交叉偶联反应结合使用。除了对映体选择性变体的有希望的初步结果外，还证明了取代的分配基团和苄基变体。
• ABC → ABCE/D Based Approaches to the Pentacyclic Ring System of the Vinca Alkaloids Using Intramolecular Hetero-[2+2]cycloaddition and Gold(I)-Catalyzed 6-endo-dig Cyclisation Protocols
  作者：Martin G. Banwell、Lorenzo V. White、Anthony C. Willis

  DOI：10.3987/com-14-s(k)19

  日期：——

  The angularly substituted tetrahydrocarbazole 13, which is readily obtained from cyclohexane-1,4-dione monoethylene ketal (6) using Fischer indole chemistry, has been converted into the isothiocyanate 16. Photolysis of this last compound affords, via an intramolecular hetero[2+2]cycloaddition reaction, the pentacyclic beta-thiolactam 17 that incorporates the ABCE ring substructure of natural products 1-3. Attempts to effect a two-carbon homologation of the four-membered ring within compound 17, and thereby establish the D-ring, failed. The azide 20, also obtained from compound 13, forms the cyclic imine 21 on thermolysis in refluxing toluene and the readily derived enamide 23 engages in a Au(I)-catalysed 6-endo-dig cyclisation reaction to give compound 24 embodying the ABCDE ring system of the title alkaloids.