(2S)-N-[9-(4-bromophenyl)-9-fluorenyl]alanine | 225098-20-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (2S)-N-[9-(4-bromophenyl)-9-fluorenyl]alanine
• 英文别名: (2S)-2-[[9-(4-bromophenyl)fluoren-9-yl]amino]propanoic acid
• CAS: 225098-20-4
• 化学式: C₂₂H₁₈BrNO₂
• 分子量: 408.294
• InChiKey: PSEQEQRXRLPLMA-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S)-N-[9-(4-bromophenyl)-9-fluorenyl]alanine 在 palladium diacetate 、 1-羟基苯并三唑 、 caesium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 N,N'-二环己基碳二亚胺 作用下， 以 甲苯 为溶剂， 反应 48.0h， 生成 N-(9-(4-morpholinophenyl)-9-fluorenyl)alaninyl-ω-N-(tert-butoxycarbonyl)lysine tert-butyl ester
  参考文献：
  名称：

  9-（4-溴苯基）-9-芴基作为安全捕捉的氮保护基

  摘要：

  9-（4-溴苯基）-9-芴基（BrPhF）基团已被开发为一种新型的安全捕捉胺保护剂。这种相对酸稳定的保护基可以通过芳基溴化物与吗啉的钯催化交叉偶联反应成功激活，然后在温和条件下使用二氯乙酸和三乙基硅烷有效裂解。互补条件报告为在存在选择性移除BrPhF组的叔丁基酯和氨基甲酸酯以及脱保护叔丁基酯和氨基甲酸酯在BrPhF胺存在。

  DOI：

  10.1021/jo0521910
• 作为产物：
  描述：

  1,4-二溴苯 在 lithium hydroxide 、 potassium phosphate 、 正丁基锂 、 lead(II) nitrate 作用下， 以 1,4-二氧六环 、 乙腈 为溶剂， 反应 40.42h， 生成 (2S)-N-[9-(4-bromophenyl)-9-fluorenyl]alanine
  参考文献：
  名称：

  A Novel Linking-Protecting Group Strategy for Solid-Phase Organic Chemistry with Configurationally Stable α-[N-(Phenylfluorenyl)]amino Carbonyl Compounds:  Synthesis of Enantiopure Norephedrines on Solid Support

  摘要：

  A novel linking strategy has been developed for synthesizing configurationally stable alpha-amino aldehyde on polymeric supports. Alkylation of L-alanine methyl ester with 9-bromo-9-p-bromophenylfluorenene, followed by ester hydrolysis and coupling to isoxazolidine, provided N-(9-p-bromophenylfluoren-9-yl)alanine isoxazolidide (5), which was transformed into its corresponding boronate 2 by a palladium-catalyzed cross-coupling reaction with diboron pinacol ester. Boronate 2 was anchored to four different polymeric aryl halides 6-9 in 70-99% yields. Polymer-bound alaninal Ib was then synthesized on non-cross-linked polystyrene by hydride reduction of isoxazolidide 10b. Treatment of alaninal Ib with phenylmagnesium bromide, cleavage of the resulting amino alcohol in a 1:2:2 TFA/CH2Cl2/anisole cocktail, and acylation with di-tert-butyl dicarbonate furnished N-(BOC)norephedrines 14 that were demonstrated to be enantiopure by conversion to diastereomeric thioureas 15 and analysis by HPLC. In summary, we have developed a process by which the 9-phenylfluoren-9-yl protecting group has been converted into a new linker for the solid-phase synthesis and manipulation of alpha-amino carbonyl compounds.

  DOI：

  10.1021/jo982413c

文献信息

• 9-(4-Bromophenyl)-9-fluorenyl as a Safety-Catch Nitrogen Protecting Group
  作者：Simon Surprenant、William D. Lubell

  DOI：10.1021/jo0521910

  日期：2006.1.1

  (BrPhF) group has been developed as a novel safety-catch amine protection. This relatively acid-stable protecting group can be successfully activated by palladium-catalyzed cross-coupling reaction of the aryl bromide with morpholine and then cleaved effectively under mild conditions using dichloroacetic acid and triethylsilane. Complementary conditions are reported for selective removal of the BrPhF

  9-（4-溴苯基）-9-芴基（BrPhF）基团已被开发为一种新型的安全捕捉胺保护剂。这种相对酸稳定的保护基可以通过芳基溴化物与吗啉的钯催化交叉偶联反应成功激活，然后在温和条件下使用二氯乙酸和三乙基硅烷有效裂解。互补条件报告为在存在选择性移除BrPhF组的叔丁基酯和氨基甲酸酯以及脱保护叔丁基酯和氨基甲酸酯在BrPhF胺存在。
• A Novel Linking-Protecting Group Strategy for Solid-Phase Organic Chemistry with Configurationally Stable α-[<i>N</i>-(Phenylfluorenyl)]amino Carbonyl Compounds:  Synthesis of Enantiopure Norephedrines on Solid Support
  作者：Francis Gosselin、Jo Van Betsbrugge、Mostafa Hatam、William D. Lubell

  DOI：10.1021/jo982413c

  日期：1999.4.1

  A novel linking strategy has been developed for synthesizing configurationally stable alpha-amino aldehyde on polymeric supports. Alkylation of L-alanine methyl ester with 9-bromo-9-p-bromophenylfluorenene, followed by ester hydrolysis and coupling to isoxazolidine, provided N-(9-p-bromophenylfluoren-9-yl)alanine isoxazolidide (5), which was transformed into its corresponding boronate 2 by a palladium-catalyzed cross-coupling reaction with diboron pinacol ester. Boronate 2 was anchored to four different polymeric aryl halides 6-9 in 70-99% yields. Polymer-bound alaninal Ib was then synthesized on non-cross-linked polystyrene by hydride reduction of isoxazolidide 10b. Treatment of alaninal Ib with phenylmagnesium bromide, cleavage of the resulting amino alcohol in a 1:2:2 TFA/CH2Cl2/anisole cocktail, and acylation with di-tert-butyl dicarbonate furnished N-(BOC)norephedrines 14 that were demonstrated to be enantiopure by conversion to diastereomeric thioureas 15 and analysis by HPLC. In summary, we have developed a process by which the 9-phenylfluoren-9-yl protecting group has been converted into a new linker for the solid-phase synthesis and manipulation of alpha-amino carbonyl compounds.