3-(4-bromo-2-nitrophenyl)-2-[2-(tert-butyldimethylsilanyloxy)ethyl]-N-(2,4-dichloro-6-iodophenyl)-N-methoxymethacrylamide | 1027600-54-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 3-(4-bromo-2-nitrophenyl)-2-[2-(tert-butyldimethylsilanyloxy)ethyl]-N-(2,4-dichloro-6-iodophenyl)-N-methoxymethacrylamide
• 英文别名: (2E)-2-[(4-bromo-2-nitrophenyl)methylidene]-4-[tert-butyl(dimethyl)silyl]oxy-N-(2,4-dichloro-6-iodophenyl)-N-(methoxymethyl)butanamide
• CAS: 1027600-54-9
• 化学式: C₂₅H₃₀BrCl₂IN₂O₅Si
• 分子量: 744.324
• InChiKey: QVKFQNWKSXSZCL-GZTJUZNOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  37
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  84.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(4-bromo-2-nitrophenyl)-2-[2-(tert-butyldimethylsilanyloxy)ethyl]-N-(2,4-dichloro-6-iodophenyl)-N-methoxymethacrylamide 、 一氧化碳 在 tris(dibenzylideneacetone)dipalladium (0) 四丁基溴化铵 、 三乙胺 、 三(邻甲基苯基)磷 、 四丁基氟化铵 作用下， 以 N,N-二甲基乙酰胺 、 四氢呋喃 为溶剂， 85.0 ℃ 、101.32 kPa 条件下， 反应 21.0h， 以51%的产率得到3'-(4-Bromo-2-nitrophenyl)-5,7-dichloro-1-(methoxymethyl)spiro[indole-3,4'-oxane]-2,2'-dione
  参考文献：
  名称：

  Synthetic Studies on Perophoramidine and the Communesins:  Construction of the Vicinal Quaternary Stereocenters

  摘要：

  An efficient synthetic strategy for installation of the two vicinal quaternary carbon centers of the communesins is reported. Key steps include the O-allylation/Claisen rearrangement of spirolactone systems, which are formed by tandem intramolecular Heck cyclization/carbonylation. Substituent and solvent effects on the stereochemical outcome of the Claisen rearrangements have been examined. The stereochemical assignment of the allyl spirolactone previously reported as 17 has now been revised to 31, which has the communesin relative configuration at the quaternary carbons. Key C-allyl spirolactone 59 bearing functional handles required for the communesin core has been constructed with a 9.8:1 diastereomer ratio.

  DOI：

  10.1021/jo061660a
• 作为产物：
  描述：

  (2E)-2-[(4-bromo-2-nitrophenyl)methylidene]-N-(2,4-dichloro-6-iodophenyl)-4-hydroxybutanamide 在 咪唑 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 3-(4-bromo-2-nitrophenyl)-2-[2-(tert-butyldimethylsilanyloxy)ethyl]-N-(2,4-dichloro-6-iodophenyl)-N-methoxymethacrylamide
  参考文献：
  名称：

  Synthetic Studies on Perophoramidine and the Communesins:  Construction of the Vicinal Quaternary Stereocenters

  摘要：

  An efficient synthetic strategy for installation of the two vicinal quaternary carbon centers of the communesins is reported. Key steps include the O-allylation/Claisen rearrangement of spirolactone systems, which are formed by tandem intramolecular Heck cyclization/carbonylation. Substituent and solvent effects on the stereochemical outcome of the Claisen rearrangements have been examined. The stereochemical assignment of the allyl spirolactone previously reported as 17 has now been revised to 31, which has the communesin relative configuration at the quaternary carbons. Key C-allyl spirolactone 59 bearing functional handles required for the communesin core has been constructed with a 9.8:1 diastereomer ratio.

  DOI：

  10.1021/jo061660a

文献信息

• Exploratory studies toward a total synthesis of the marine ascidian metabolite perophoramidine
  作者：Michael A. Evans、Joshua R. Sacher、Steven M. Weinreb

  DOI：10.1016/j.tet.2008.10.060

  日期：2009.8

  A strategy for a total synthesis of the marine alkaloid perophoramidine has been investigated. Key steps which have been tested include a tandem intramolecular Heck/carbonylation reaction and a stereoselective allylation of a pentacyclic δ-lactam to produce the C-4/20 vicinal quaternary centers having the requisite relative configuration of the metabolite.

  已经研究了海洋生物碱过邻苯二甲酰胺全合成的策略。已测试的关键步骤包括串联分子内Heck /羰基化反应和五环δ-内酰胺的立体选择性烯丙基化，以产生具有必需的代谢物相对构型的C-4 / 20邻位四级中心。