tert-butyl Nα-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine | 863766-49-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: tert-butyl Nα-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine
• 英文别名: tert-butyl (2S,3S,4R)-5-amino-2-(9H-fluoren-9-ylmethoxycarbonylamino)-3,4-dimethyl-5-oxopentanoate
• CAS: 863766-49-8
• 化学式: C₂₆H₃₂N₂O₅
• 分子量: 452.55
• InChiKey: RJDNRDNAZPOUIG-DMPWYTOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  108
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl Nα-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以93%的产率得到Fmoc-DiMeGln
  参考文献：
  名称：

  Synthesis of N-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine: An Application of Lanthanide-Catalyzed Transamidation

  摘要：

  N-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine (6) was synthesized from tert-butyl N-Boc-(2S,3S,4R)dimethylpyroglutamate (13). This synthesis involved selective deprotection of a Boc group from a lactam nitrogen in the presence of a tert-butyl ester, Fmoc protection of the lactam, and a lanthanidecatalyzed transamidation reaction of the Fmoc-protected lactam, using ammonia and dimethylaluminum chloride. The scope of Lewis acid-catalyzed transamidation of acylated lactams was explored through the variation of lanthanide, lactam, acyl group, amine, and aluminum reagent. The reactivity of various metal triflates was found to vary in the following qualitative order: Yb Sc > Er similar to Eu similar to Sm > Ce similar to Agl > Cu-II similar to Zn. Intriguingly, catalysis was only observed when ammonia was the nitrogen nucleophile; addition of other amidoaluminum complexes to acyl lactams was found to be insensitive to the addition of lanthanides.

  DOI：

  10.1021/jo050518r
• 作为产物：
  描述：

  tert-butyl N-Fmoc-(2S,3S,4R)-3,4-dimethylpyroglutamate 在 europium(III) trifluoroacetate 、 氨 、 二甲基氯化铝 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以77%的产率得到tert-butyl Nα-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine
  参考文献：
  名称：

  Synthesis of N-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine: An Application of Lanthanide-Catalyzed Transamidation

  摘要：

  N-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine (6) was synthesized from tert-butyl N-Boc-(2S,3S,4R)dimethylpyroglutamate (13). This synthesis involved selective deprotection of a Boc group from a lactam nitrogen in the presence of a tert-butyl ester, Fmoc protection of the lactam, and a lanthanidecatalyzed transamidation reaction of the Fmoc-protected lactam, using ammonia and dimethylaluminum chloride. The scope of Lewis acid-catalyzed transamidation of acylated lactams was explored through the variation of lanthanide, lactam, acyl group, amine, and aluminum reagent. The reactivity of various metal triflates was found to vary in the following qualitative order: Yb Sc > Er similar to Eu similar to Sm > Ce similar to Agl > Cu-II similar to Zn. Intriguingly, catalysis was only observed when ammonia was the nitrogen nucleophile; addition of other amidoaluminum complexes to acyl lactams was found to be insensitive to the addition of lanthanides.

  DOI：

  10.1021/jo050518r

文献信息

• Synthesis of <i>N</i>-Fmoc-(2<i>S</i>,3<i>S</i>,4<i>R</i>)-3,4-dimethylglutamine: An Application of Lanthanide-Catalyzed Transamidation
  作者：Selçuk Çalimsiz、Mark A. Lipton

  DOI：10.1021/jo050518r

  日期：2005.8.1

  N-Fmoc-(2S,3S,4R)-3,4-dimethylglutamine (6) was synthesized from tert-butyl N-Boc-(2S,3S,4R)dimethylpyroglutamate (13). This synthesis involved selective deprotection of a Boc group from a lactam nitrogen in the presence of a tert-butyl ester, Fmoc protection of the lactam, and a lanthanidecatalyzed transamidation reaction of the Fmoc-protected lactam, using ammonia and dimethylaluminum chloride. The scope of Lewis acid-catalyzed transamidation of acylated lactams was explored through the variation of lanthanide, lactam, acyl group, amine, and aluminum reagent. The reactivity of various metal triflates was found to vary in the following qualitative order: Yb Sc > Er similar to Eu similar to Sm > Ce similar to Agl > Cu-II similar to Zn. Intriguingly, catalysis was only observed when ammonia was the nitrogen nucleophile; addition of other amidoaluminum complexes to acyl lactams was found to be insensitive to the addition of lanthanides.