ethyl (R)-1-(1-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-(trimethylsilyl)penta-3,4-dien-2-yl)-1H-pyrrole-2-carboxylate | 1566557-44-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: ethyl (R)-1-(1-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-(trimethylsilyl)penta-3,4-dien-2-yl)-1H-pyrrole-2-carboxylate
• 英文别名: ethyl 1-[(2R)-1-(9H-fluoren-9-ylmethoxycarbonylamino)-3-trimethylsilylpenta-3,4-dien-2-yl]pyrrole-2-carboxylate
• CAS: 1566557-44-5
• 化学式: C₃₀H₃₄N₂O₄Si
• 分子量: 514.696
• InChiKey: AQGXQUMIPGFJOT-HHHXNRCGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.33
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  69.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (R)-1-(1-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-(trimethylsilyl)penta-3,4-dien-2-yl)-1H-pyrrole-2-carboxylate 在 溴 、 溶剂黄146 作用下， 反应 1.0h， 以63%的产率得到ethyl (S)-1-(1-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-5-bromopent-3-yn-2-yl)-4,5-dibromo-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  NHC–Cu-Catalyzed Addition of Propargylboron Reagents to Phosphinoylimines. Enantioselective Synthesis of Trimethylsilyl-Substituted Homoallenylamides and Application to the Synthesis of S-(−)-Cyclooroidin

  摘要：

  A catalytic method for the efficient and enantioselective addition of a 1-trimethylsilyl-substituted allene moiety to phosphinoylimines is presented. Transformations are promoted by 5.0 mol % of a copper complex of an N-heterocyclic carbene in the presence of a propargylboron reagent that can be readily prepared in multigram quantities. Within 10 min of reaction, products are obtained in up to 91% yield, 98% allene (vs propargyl) selectivity, and 98:2 enantiomeric ratio. An assortment of aldimines serve as suitable substrates. The phosphinoyl and silyl groups can be removed efficiently and orthogonally. The silylallene moiety may be transformed to versatile derivatives that are difficult to access via nonsilylated allenes. The special features and utility of the approach are highlighted through a succinct enantioselective synthesis of marine alkaloid S-(-)-cyclooroidin.

  DOI：

  10.1021/ja500373s
• 作为产物：
  描述：

  2-氧代-5-己酸乙酯 在 盐酸 、 臭氧 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 1.08h， 生成 ethyl (R)-1-(1-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-(trimethylsilyl)penta-3,4-dien-2-yl)-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  NHC–Cu-Catalyzed Addition of Propargylboron Reagents to Phosphinoylimines. Enantioselective Synthesis of Trimethylsilyl-Substituted Homoallenylamides and Application to the Synthesis of S-(−)-Cyclooroidin

  摘要：

  A catalytic method for the efficient and enantioselective addition of a 1-trimethylsilyl-substituted allene moiety to phosphinoylimines is presented. Transformations are promoted by 5.0 mol % of a copper complex of an N-heterocyclic carbene in the presence of a propargylboron reagent that can be readily prepared in multigram quantities. Within 10 min of reaction, products are obtained in up to 91% yield, 98% allene (vs propargyl) selectivity, and 98:2 enantiomeric ratio. An assortment of aldimines serve as suitable substrates. The phosphinoyl and silyl groups can be removed efficiently and orthogonally. The silylallene moiety may be transformed to versatile derivatives that are difficult to access via nonsilylated allenes. The special features and utility of the approach are highlighted through a succinct enantioselective synthesis of marine alkaloid S-(-)-cyclooroidin.

  DOI：

  10.1021/ja500373s